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REFINERY PROCESS MODELING

APractiall Guide
to Steady State Modeling
01 Petroleum Processes

FIRST EDITION
REFINERY PROCESS MODELlNG

A Practical Guide to Steady State Modeling


I
,I
of Petroleum Processes
(Using Commercial Simulators)
i
I First Edition

Gerald L. Kaes

Consulting Chemical Engineer


Chemicall'rocess Simulation
Colbert, Georgia

The Athens Printing Company


Athens, Georgia
Refinery Process Modeling

First Edition

ISBN: 0-9679274-0-4

Copyright ()2000 by Kaes Enterprises, Inc.


All rights reserved. Printed in the United States of America.
This book or parts thereof may not be reproduced
in any form without permission.

Published by:
Kaes Enterprises, Inc.
522 Kingston Road
Colbert, Georgia 30628
Phone: (706) 788-3366
FAX: (706) 788-3366
emaiI: KAESENTER@aol.com

First printing: March 2000

The In/orma!ion contained in this book is believed to be accurate and reasonable. However, the author
and;: aes Er.!erpri5cs, Inc. do not guarantee the accuracy or completeness of any in/ormatioll published
herelf1 and sha!t nol be responsible Jor any errors, omI5:,-;on5. -or damages arising out of the lIse oJthis
rn/orfTlQfi0n Titls book is published with the intent tn supply infurmation and is no! an attempt lo render
('ng; ,':eenng or other professional services. The user of infon,l(J[ion published herein is solely responsible
for .he acc;JrC0' and appl;cability ofcalculations based on this information.
They say that behind every good man is a good woman. Anything good I have
accomplished I owe to my wife Barbara who has encouraged and supported me these
many years. This book is lovingly dedicated to her.

f
F'-
At the urging of several colleagues, I decided to record many of the tips and tricks for
computer simulation of petroleum processes I have amassed over the past thirty-eight
years. In this way, perhaps I can partially repay the technical debt I owe to the many
engineers who helped me develop my skills as a young engineer. I was fortunate to begin
my career in an era when corporations sought to develop young engineers through
intensive training and apprenticeship programs. Unfortunately, the bottom line thinking
of today no longer allows such an approach. The young engineer is otlen thrust into a
plant environment with little or no training. Hopefully, this book will serve 10 some
small capacity to provide some practical training for the younger engineers.

If you are looking for technical elegance this may not be the book for you. Frankly, in
my experience with modeling petroleum refinery processes (with commercial simulators)
I have encountered little that is elegant. I chose to focus onthe more practical aspects of
engineenng. Engineering theory is good and necessary; however, it is based on perfect
processes and simplifying assumptions. Any practicing engineer knows it is necessary to
apply experience factors to reconcile theoretical expressions with real world processes.
This is the fOCllS of this book.
I
It is noteworthy to remind the reader that this book was written for steady state models
for petroleum processes. By definition, for a steady state process, there is always" f
perfect mater'ial balance and heat balance. Any engineer who has conducted a plant test I
knows that real plants seldom operate at steady state. This must always be taken into
consideration when developing steady state models. I
I must also stress that this book was written for engineers who use commercial software
for their simuiation efforts. Because of the enormous overhead associated with
developing and maintaining simulation software, most corporations today have
I
abandoned their own efforts in favor of a vendor-supplied simulation program. While
this is the most cost-effective approach, it is not always the best technical approach.
Commercial simulators must be based on open literature methods. This does not allow
the use of proprietary data that might be useful in improving the accuracy of simulation
I
results ~

\:everthe!ess. it is possible to develop accurate and useful models for petroleum


processes ..,ith commercial simulators. The author has had extensive experience with the
Hyprotecr.. Lld HYSIM, and HYSYS programs, and the SimSci PROVISION" program.
Howc\cr. 'he principles in this book are not simulator specific and may be applied with
any simuialOf having tne features required for simulation of petroleum processes.

GcraIJ L Kaes

:
TABLE OF CONTENTS

Chapter 1 - Introduction to. Steady State Simulation ......................... I


1.1 The Steady State Process ................................ .. ................... I

1.2 Dynamic Simulation .................... ....................... ............. .......................... 2


1.3 Steady State Simulation Program Features ....................................................... 3
1.3.1 Pure Compon(!nt Data Library ...................... .............. ........... .. ................ 3
1.3.2 Non-Library Components ............................................................................ 4
1.3.3 Thermodynamic Methods ............................................................................. 4
1.3.4 Physical and Transport Properties ........................................... ,.............. :....... 5
1.3.5 Simulated Laboratory Tests....... ............... ............... ............. ....... 5
1.3.6 Unit Operation Calculations ......... .................... .. ................................ 5
1.3.7 Special Flow Sheet Modules........ .................... ................ ....... 6
1 .3.8 Graphical Interface...................... ..................................................... -/
1.4 Steady State Simulation Programs.................... .. .......................................... 7
Chapter 2 - Composition of Petroleum Refinery Feed Stocks ............................... 10
2.1 Crude Oil Properties ........................................................ . . 10
2.2 Crude Oil Composition........ .................................. .. ............................... 13
2.3 Crude Oil Assay....... ................................. ....................................... .... 13
ff 2.4 Crude Oil Blending ................................. .. .. 14

! Chapter 3 - Laboratory Testing of Petmleum Streams ........................................ 16


3.1 True Boiling Point Distillation (TBP) ........................................................... 16
3.2 ASTM 086 Distillation ................................................................................. 17
3.3 ASTM 01160 Distillation ............................................................................. 18
3.4 API Gravity ............................................ . ................................ 19
.j 3.5 Reid Vapor Pressure (R.V.P.) ................. .. ...... ~ ......................... 19
3.6 Chromatographic Simulated Distillations.. ...... . ...... 20
3.7 Flash Point ........... ............ . ......... . ................................. 22
1:.
.~) 3.8 Pour Point ............................ .. ................. 22
')-
3.9 Viscosity .......................... . ................................. _J

'i 3.10 Octanes ............................. . .......................................... 23


3.11 Cetane ................... . ................ '>'
L-'

Chapter 4 - Developing Petroleum Pseudo-components ............................................ 25


4.1 Pseudocomponent Normal Boiling Points ......................................................... 25
4.1.1 Conversion O'fD86 DistillatIons ....................................................... :..... 26
4.1. L I 086 Cracking Corrections .............................................................. 28
5
TABLE OF CONTENTS (continued)

4, I ,2 Conversion of D I 160 Distillations"""",." ""'''''''''''''''''' """,," ." .. " "".". ".29


4.1.3 Conversion of Simulated Distillations ".".""."""".""".".".,,"",, .... ,," ".",29
4.1.4 Selection of TBP Cut-point Ranges .. """"",,, .. ,,.,,,,.,,.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,.,, 31
4,2 Development of Pseudo-component Gravities" ".",,'" ""'''''''''''''''''''''''''''' .33
4,3 Development of Pseudo-component Molecular Weights ""'"'''''''' """"".' .. 35
4.4 Pseudo-component Enthalpies and Critical Propenies "'''''""".""".""""". """ 36
Chapter 5 - Limitations of Petroleum Pseudo-components .................................. 37
. 5. I Prediction of Laboratory Distillations"""""" " ....... """"""",:.. ,,""",.,,"",, .. ,,'" 37
5.2 Prediction of True Stream Composition '"''".".".".,,''' .... ".,.,"""""',.", ... ,38
5,3 Simulation of Refinery Reactors """ ... "".""."",,.,,'" ",,,,,,,,,.,,,,, ... ,, .. ,,,39
5.4 Simulation of LlIboratory Tests "'''''''''''''''''''''''''''''''''''''''''''''''' "".""".,, " .. ,,", 40
Chapter 6 - Thermodynamics for Petroleum Calculations ........................... 43
6.1 Equilibrium K Values .... _.... __ ................................. _ ......... 43
6,2 Effect of Non-Hydrocarbons on K values",,,,,,,,,,,,.,,,,, """"" ,",,"""'''' ,.""".,44
6.3 H ydrocarbon-Water Systems"",,,,,,,,,,,,, ."." ... " """"""" "".".""".""""".", 4 5
6,4 Enthalpies". ",,"" "".""""""",,,,,,,,,,,,, '" ."."""."." '" """."."."",,"""." ,,46
, ":.;~~
6,5 Recommended Methods for Petroleum Systems .. " .. ,," """"""""""""",,,,, ".46
6,6 Thermodynamic "Rules of Thumb""""""". .... ".".,"',.,",""',.,' ..... 48
Chapter 7 - Practical Distillation Principles ........................................................ ".52
7.1 Theoretical Considerations"""" ."., "".,,"" "" ... """."",,""''', 52
7,1.1 Inside-out Distillation Algorithm "".""" ..... ",,. '''''''".""."".".,,'''',,' """" 53 }
'.1
7. 1.2 Column Conventions"."""""" """"".". "" ,,,,,,,,,""''',, """"""."""",,,.,,,, 54
:i
7, I ,3 Initial Solution Estimates" """ """ "" ". "".,,"'" ""," "" """ """""",,, "" "" 56 ,

7.1.4 Non-converged Column Solutions ",,""",,"'''''''' ""'""""""."",,"" """.56


7.2 Simulation of Existing Columns .. """"""", .. """".,,"",,"",,. """~'" 58
7.2, I Gathering the Information".""""", """"""" "","""""" .... "",,""",, 58 "
7,2,2 Defining the Separation Zones ".",,""''',,'''''' .. """"""""""",,.,,""",, S9
7,2,3 Translation of Actual trays to Theoretical Trays. """"""""" ,," ,,,,,,,,,,64
7,2.4 Defining Performance Specifications" ,,,,,,,,,,, """""'" """""""",67
7.2.5 Tray Rating ""''''''''''''''",'' .. "",,",,. """"".". """" 71
7,3 Troubleshooting Actual Columns """""", . "","" 72
7,3.1 Difficulties Matching Real Column Operations ,,,,,,72
7,3,2 Diagnosis of Column Operational Problems, "''''''", """"",76
Chapter 8 - Crude Distillation ....... "" ......................................................................... 81
8.1 Crude Distillation Units General Information.".""""". """.""""""""",,.,, "",82
8,1.1 Process Description '''"" ".",,""" ."""."".",,. """"""."."",,. "."""".83
8. 1. 2 Typical Ope, at ions and Control "" ..... """.".,, "."""."""."'" .".,," 87
6

'1
TABLE OF CONTENTS (continued)
. C apacny
8.1.3 Schemes to Increase C rude Processmg . ........................................
. . 90
8.1.3.1 Main Column Considerations .............................................................. 90
8.1.3.2 Furnace Capacity Considerations ........................................................ 93
8.2 Crude Distillation Units: Simulation of Existing Columns .......... __ ........ __ ........... 95
8.2.1 Definition of the Crude OiL.......... . ............................................. 95
8.2.1.1 Crude Assay Data............ ........... ..... . ......... . ............. 95
8.2.1.2 Crude Oil Data from Product Blending ... ..................................... " 98
8.2.2. Collection of Operating and Laboratory Data .......................... . ..... 106
8.2.3 Translation of Actual Trays to Theoretical Trays ................................... 108
8.2.3.1 Main Column Stripping Zone ........................................................... 109
8.2.3.2 Main Column Flash Zone......... . ......................................... 109
8.23.3 Main Column Wash Zone ............ __ . . . . . ...................................... 110
8.2.3.4 Pumparound Zones ....................................................................... 110
8.2.3.5 Side Product Draw Zones.,................ . . . ....................................... 112
8.2.3.6 Top Section of Main Column ........................................................... 112
8.23.7 Side Stripping Columns .............................................................. 113
8.2.4 Crude Column Overhead System ........................................................... 113
~.25 Solution Techniques: Inside! Out Column Algorithm ............................... 114
8.2.5.1 Initial Estimates ..................................... ........................................ liS
8.2.5.2 Initial Model Phase................................ ................................... 115
8.2.5.3 Tuning the Model ......................................................................... 116
Chapter 9 - Vacuum Distillation ............ _................................................................. 119
9.1 Vacuum Distillation: General Information .......... ........................... ____ ... __ ... 119
9.1.1 Process Description .......... __ .... __ .... __ ..... __ ... . . . ... __ .............. __ .. __ ..... __ .... __ 119
9. I .2 Typical Operations and Control... .. __ .... __ .......... __ ............ __ .... __ .... __ ...... 123
9.2 Vacuum Distillation Units: Simulation of Existing Columns ... __ .. __ ........ __ ..... __ .. 129
9.2.1 Definition of the Topped Crude Oil .. ____ ....... __ ............... ____ .. ____ .... __ .... __ ... 129
9.2.1.1 Crude Assay Data ____ .. __ .................. __ ... .. .............. __ ........... :............ 130
9.2.1.2 Topped Crude Oil Data from Product Blending................................. 130
9 2. I.3 Molecular Weight Estimation .... ............ .............. ...................... . 131
9.2.2 Adjustments to the Topped Crude Oil. ............................................ 131
9.2.3 Collection of Operating and Laboratory Data ................~.. .. ............. 134
9.2.4 Translation of Actual Configuration to Theoretical trays ......................... 135
9.2.4.1 Steam Stripping Zone for Wet Vacuum Units ................................... 136
92.4.2 Boot Cooler Circuits.......... .............. .. ................................. 136
9.2.4.3 Light Gas Oil Zone .............. . ......................... 137
9.2.4.4 Heavy Gas Oil Zone ............. . .. .................... 138
9.2.4.5 Wash Grid and Flash Zone.... .. __ .............. 138
9.2.5 Solution Techniques: Inside/Out Algorithm ....................................... 140
92.5.1 Initial Estimates ................. . ........... ...................... 141
92.5.2 Initial 1--10del Building Phase............. ................ ...141
9.2.5.3 Tuning the Model .............. . . ............................. 145
Chapter 10 - Refinery Reaction Systems .................................................................. 148

7
TABLE OF CONTENTS (continued)

10.1 Reactor Processes- General Information ......................................................... 148


10.1.1 CatalyticCracking ........................... ~ ................................................, .... 150
10.1.2 Hydrocracking and Hydrotreating ........................................................... 153
10.1.2.1 Hydrocracking ................................................................................ 153
10.1.2.2 Hydrotreating ................................................................................. 157
10.1.3 Reforming and Isomerization .................................. ............. ............. 160
10.1.3.1 Catalytic Reforming ......................... ............ .160
10.1.3.2 Isomerization ............................................................................. 164
10.1.4 Alkylation and Polymerization .............................. .. .................. 167
10.1.4.1 Alkylation ................................................................................... 167
10.1.4.2 Catalytic Polymerization................................ ............. .. ............ 172
10.1.5 Thermal and Coking ........................................~........ . ......... , ....... 174
10.1.5.1 Visbreaking ............................................................................... 174
10.1.5.2 Coking............................................................... ............. 178
10.1.6 Hydrogen Plants ......................................... :............... . ............. 181
10.1.7 Ether Processes .................................................................................. 183
10.1.7.1 MTBE Processes ......................................................................... 183
10.1.7.2 TAME Processes........................................... .. ............. 186
10.J Reactor Processes: Simulation Techniques........................... ... .. ..... 188
JO.2.1 Black Box Reactor Mode!... ....................................................... :........ 188
10.2.2 l\1odified Black Box Reactor ................ ........................... .. ........... 190
10.2.3 Empirical Predictive ReactoL....... ....... ................... .......... .. ........... 193
10.2.4 Free Energy Minimization Reactor (Gibbs) ............ .. ........... 196
10.2.5 Equilibrium Reactor .............................................................................. 198
10.2.6 Stoichiometric Conversion Reactor ................... ............. ....... 200
Chapter 11 - FCC (Fluid Catalytic Cracking) Processes ........................................ 204
I
ILl FCC Proces,,,s: Generallnformation ........................................................... 204
I
11.1.1 Process Description ............................. ................... ............ .. ............... 205
I 11.1.2 Typical Operations and Control.. .......................................................... 207
11.1.2.1 FCC Reactors .............................................................. .. ..... 208
11.1.2.2 Main Fractionators........................................ .. .............. 208
11.1.2.3 Slurry Strippers............................................... . ........... 211
11.1.2.4 FCC Gasoline Splitters................................... ..~ .... 2!2
11.1.2.5 FCCGasPlants........................................ . .... 212
11.2 FCC Processes: Simulation of Existing Units .............. .. .. 217
11.2.1 Definition of the Reactor Effiuent... ..................... . . .... 217
11.2.2 Collection of Operating and Laboratory Data ..... . .. 220
11.2.3 Reactor Modeling ......................................... .. . . . . ......... 222
112.4 Main Fractionator ............................................... . .. .... 223
11.2.4. I Quench (Desuperheating) Zone .................................. . .. .. 224
112A2 Heavy Cycle Oil Zone ................................ .. .... 225
11.243 Light Cycle Oil Zone................................. . .......................... 226
11.244 Heavy Naphtha Zone ....... ...................... . .................... 227
11.2.4. 5 Overhead System ......................................... .. .............. 228

8
TABLE OF CONTENTS (continued)

11.2.5 Gas Plant Columns ...................... :......................................................... 229


11.2.5.1 Primary Absorber.. ......................................................................... 229
11 .. ' er ........................................................... .
2 5 ' 2 St npp .............. 230
11.2.5.3 Secondary Absorber............................ ........... ........... .. .... 230

I 11.2.5.4 Stabilizer.......................................................
11.2.5.5 C3! C4 Splitter............................................... ...... .....
. ............. 23)
.. ....... 23]
1 11.2.6 Recycle Loops............................................... . .... 232
I 11.2.6.1 Recycle Estimates............................... ........... .
11.2.7 Solution Techniques: Inside! Out Column Algorithm...
.. ....... 232
...... 233
! I 1.2.7. I Initial Estimates: Main Fractionator.. ..... ...........
I i .2.7.2 Initial Estimates: FCC Gas Plant Columns ......
.. ...... 233
...: .... 233
11.2.7.3 Initial Model Phase ..................................................................... 234
11.2.7.4 Tuning the ModeL......................................... . . ....... 234
Chapter 12 - Catalytic Reforming Processes ............................................................ 236
12.1 Catalytic Reforming Processes: General Information ........ .......................... 236
12. I. I Process Description ............................................................................. 237
12.1.2 Typical Operations and Control.......... ........... .. ............................ 239
12.1.3 Catalytic Reformer Reactors....................................... . .......... 241
12.1.4 Reformer Separator Operations............................ ............... . .. ....... 242
12.1.5 Stabilizer Tower Operations .................................... .. ... 242
12.2 Catalytic Reforming Processes: Simulation of Existing Units... .. ............ 243
12.2.1 Definition of the Reactor Effiuent... .................................................... 243
12.2.2 Collection of Operating and Laboratory Data . . . . . . . . . . . . ......... 245
12.2.3 Reactor Modeling............. .............................. .. ...... 246
12.2.4 Stabilizer Modeling .......... ................................... .. ......................... 248
12.2.5 Recycle Loops.......................................................... .. ................ 248
12.2.5.1 Recycle Estimate ...... ... .................................. .. .................... 249
12.2.6 CCR Catalyst Systems........................................... .. .................. 249
12.2.7 Solution Techniques ........................................................................... 249
12.2.7.1 Blocked Operations ..................................................................... 250
Ch apter 13 - Hydrogen Processes ........................................................................ 251
~

13.1 Hydrotreating Processes: General Information .... . .. ................. 251


13. 1.1 Hydrotreating: Process Description ............. .. .. ...................... 252
13 I 2 Typical Operations and Control.. ............... .. .. .......... 253
13 I 3 Hydrotreating Reactors .......... . .............. 255
13. I .. Separators! Gas Treating .......................... .. . ........ 255
! 3 I 5 Product Stabilizers (Strippers) ...................... . .. .... 256
13 2 H\drotr~ating Processes: Simulation of Existing Units....... .................. 256
13.2 I Definition of the Reactor Effillent.................... . .......................... 256
13.22 Collection of Operating and Laboratory Data ............. .. 258
13.2.3 Reactor Modeling............ ............ .. .................. 260
13.24 Modeling Separators! Gas Treating....... .. .................... 262
132.5 Modeling Stabilizer (Stripper) Columns... .............. . ..................... 262

9
),:

- TABLE OF CONTENTS (continued)


It
13 .2.6 Recycle I Purge Gas Calculations ......................................................... 263
13.2.6.1 Initial Estimate for Recycle Hydrogen............................................. 264
13.i.7 Solution Techniques ........... ~ ................................................................. : 265
13.2.7: I Blocked Operations..................................................................... 265
13.3 Hydrocracking Processes: General Information .......................................... 266
13.3.1 Hydrocracking: Process Description................. .266
13.3.2 Typical Operations and Contro!........... .. ............................ '267
13.3.3 Hydrocracking Reactors.................. . .......................................... 269
13.3.4- Separators! Gas Treating.......................................................................... 269 ;
13.3.5 Quench Hydrogen ............................................................................ 270
13.3.6 Product Separation ......................................................................... 270
13 A Hydrocracking Processes: Simulation of Existing units ............,.. ............ .. 270
13.4.1 Defmition of the Reactor Effiuent......................... ...............................271
13.4.2 Collection of Operating and Laboratory Data ......................................... 272
13 A.3 Reactor Modeling ................................................................................. 274
13A.3.1 Heat of Reaction ........................................................................... 276
\3 A. 3. '2 Reactor Calculations for the Design Case.. .................... '277
13.4.4 Modeling Separators! Gas Treating......................................... .279
13.4.5 \<odeling Fractionation Columns..................................... 279
13.4.6 Recycle / Purge Gas Calculations ............................................. . ... 280
13A.6.1 Initial Estimate for Recycle Hydrogen ...................................... 280
13 A.6.2 Recycle! Quench Hydrogen Techniques ........................................ 281
13.4.7 Solution Techniques .............................................................................. 282
13.4. 7.1 Blocked Operations................... .. .............................. 282
13 S Hydrogen Plants: General Information ...... ................. 283
1351 Hydrogen Plants: Process Description .................................. 283
1~. 5.2 Typical Operation and Control........ ......... ..... .'. 284
13.5.3 Hydrogen Plant Reactors..................... .. ..................... 286
13.5A Energy Recovery ............................................................................... 287
13 6 Hydrogen Plants: Simulation of Existing Units .................... 288
13.6.1 Collection of Operating and Laboratory Data. ................................ 288
13.6.2 Modeling Reactors in Hydrogen Plants .... . ............
, .289
13.6.3 Mode\ing Amine Treaters ......................... .. .. ......................... 290
13.6A \1odeling PSA Units ....................................... . .. ........................ 290
13.6.5 Steam! Water Systems ................... . ................. 290
Chapter 14 - Thermal Processes ............................................................................... 292
l~ 1 Visbreaking: General Information ... ................................. 292
i": I 1 \'isbreaking: Process Description .... 293
\..: 1.2 Typical Operations and ControL...... .......... .. 294
1..: 1.3 \'i sb reak'109 R eactlOns
. ...................... . .296
142 Product Separation ............................................................................... 296
14: Visbreaking Processes: Simulation of Existing Processes ................ . 296
.. ~

10

';',
TABLE OF CONTENTS (continued)

14.2.1 Definition of the Soaker Outlet... ............................................. , .. , .. 297


14.2.2 Collection of Operating and Laboratory Data: ............. ................ . ... 298
14.2.3 Reaction Modeling ............................................................. ....... 299
f 14.2.4 Modeling Fractionator Columns .................................. . .. }OO

I ~
14.3 Delayed Coking: General Information.........................
14.3.1 Delayed Coking: Process Description .............. .......... .
14.3.2 Typical Operation and Control.. ..................
........ 30 I
. .. 30 I
. .. 302
14.3.3 Coking Reactions .........................".............. .. ......... . ...... 303
14.3.4 Product Separation ........................................ ... 30}
14.4 Coking: Simulation of Existing Processes ........,............... . . ..... 304
14.4.1 Definition of the Coke Drum Outlet (Reactor Effiuent) ... 304
14.4.2 Collection of Operating and Laboratory Data: ..... 307
14.4.3 Reaction Modeling ................................................... . ... 308
14.4.4 Modeling Main Columns ..................................... . . ... 309

Chapter 15 - Alkylation Processes ....................................... ' .................................... 311


15. I Alkylation Processes: General Information ..... ....... ...... .... 3 I I
15.2 Alkylation Processes: Process Description ..... ....... ...... ... .... . ..... 3 I I
15.2. I Process Description: HF Alkylation Units .............. .3 13
15.2.2 Process Description: H 2S04 Alkylation Units ......... .................... .315
15 3 Alkylation Processes: Typical Operations and Control ...................... . . .. 318
153.1 Typical Operations and Control: HF Processes ........ . .318
15.3.2 Typical Operations and Control: H2S0. Processes ...... . ... 319
I 5~ Alkylation Reactors ........................................... . .321
! 5.4.1 Reactors: HF Processes .............................. . .321
15.4.2 Reactors: H2S0. Processes .... ...................... . .......... . .322

I
f
15.5 Product Separation .......................................... .
156 Alkylation Processes: Simulation of Existing Units ..
15.6. I Definition of the Reactor Effluent .................. .
! 5.6.2 Collection of Operating and Laboratory Data .. .
r 56} Reactor Modeling ...
.........
,J_J
7'
'7'
. .J_J

. .. 326
328

!
15.6.3.1 HF Reactors......... .......... . .329
15.6.3.2 H 2SO, Reactors . . . . . . . .......... . .329
: 5.6.4 Modeling the Acid Systems.... ............ . .331
f
;
1565 Modeling of Distillation Columns .. .333
!; 1565. I Propane HF Strippers .... ........ . 333
). J 56.5.2 Depropanizers.. .. ............. .. 335

I 156.5.3 Deisobutanizers in /hSO. Processes.


15 6.5.4 Isostrippers in HF Processes ..
15.6.5.5 Debutanizers ............... ..
..... 335
.336
".. 337
15.6.56 Alkylate Splitters ...... . .337
i 566 Modeling of Recycles .. ".. 338
.. p.locesses ......................................................................
Chapter 16 -,\1'(sce II aneous - --,...- 341
.
/1
TABLE OF CONTENTS (continued)

16.1 Processes That May Be Modeled with Commercial Simulators ...................... 341
16.1.1 Catalytic Polymerization ........................................................................ 341
16.1.1. I Catalytic Polymerization: General Information .............................. 342
16.1.1.2 Catalytic Polymerization: Simulation Techniques ........................... 343
16.1.2 MTBE Processes ..................................................... ............... 344
16.1.2.1 MTBE Processes: General Information ........................................ 345
16.1.2.2 MTBE Processes: Simulation Techniques .............. . .................. 347
16.1.3 TA.t\1 Processes .................................................................................. 349
16 1.3.1 TAME Processes: Generallnformation........ ..350
16.1.3.2 TAME Processes: Simulation Techniques ..................................... 351

~
.4 Amine Treaters ........................................................................................ )52
16.1.4.1 Amine treaters: General Information ............................................... 352
16.1.4.2 Amine Treaters: Simulation Techniques .......................................... 356
16.2 Processes for Which Commercial Simulators Are Inadequate ....................... 358
16.2.1 Asphalt Processes ............................................................................. 359
16.2.2 Lubricating Oil Processes .................................................................... 359
16.2.3 Aromatic b:traction .............................. . ......................... 360
16.2.4 Chemical Treatment Processes ......................... . ....... 360
16.2.5 Diffusion! Adsorption Processes... .................................. ..... 361
Appendix A. - Glossary .............................................................................................. 363
Appendix B - Reference:s ........................................................................................... 379
Appendix C - Subject Indel ..................................................................................._387
Biography of Author .................................................................................................. 39i

12
Chapter 1 .
In trod uction to Steady State Simulation
The modcling. techniques in this book are for steady state simulation. The steady state
concept has been applied widely in chemical engineering to the design and evaluation of
individual unit operations and processes consisting of multiple unit operations. While
~ecent advances in computer technology have made possible the use of dynamic
simulation for large process flow sheets, steady state simulation continues to be the major
tool for ane.lysis and design of chemical processes.

The development and maintenance of general purpose simulation programs is costly, and
most engineering 'contractors and operating companies have abandoned their efforts in
favor of licensing or purchasing commercially developed software'.. The commercial
software is cost effective; however, it may represent a compromise in technology since
only openliterature and vendordevelopedmethods are provided. To overcome these
limitations, a licensee may have a vendor incorporate proprietary methods and data into a
pri\'ate version of the software.

A major advantage of commercial software is stanJardization of methods and data.


Common software is available to both engineering contractors ~nd operating companies.
Therefore, plant design models may be constructed using the simulation program of
choice for an operating company. For companies with mUltiple sites, the use of the same
program at all sites provides a measure of standardization and also minimizes training
costs.

Commercial steady state simulation software is well established in the marketplace.


There are many commercial programs available that may be used to model the petroleum
processes. The techniques presented in this book are generally not simulator specific and
ma\' be applied to any commercial simulator program which has the features necessary to
model the petroleum processes.

1.1
The Steady State Process
B\ definition, 2:1y chemical process has a perfect material and heat balance in the steady
;'.ale This pri~.ciple also applies to the individual unit operations within the process.
Th2t IS, the law of conservation of mass is perfectly upheld, and every unit of mass
en:ering the prccess in the feed stocks leaves the process in the products. Only in the
C23e of a chemical reaction is mass transformed; however, for this case the total units of
mcss entering and leaving the process are still the same. For many oj Ihe petroleum
re(JClOrs, some mass is converted 10 coke which is deposited on Ihe cata{vst. This mass
ieaves the reacllon separately from the other reaction products and it must be considered
!
i
when caicuiall":? Ihe mass balance jor the process.

L --'-
2 Introduction to Steady State Simulation

The heat or energy.balance is also perfect for a steady state process. That is, the units of
energy entering the process in the feed stocks and other heat sources such as process
heaters must leave the process in the products and heat sinks such as coolers. The
'I
principle also applies to chemical reaction within the process, where the reaction heat is
supplied for endothermic reactions and removed for exothermic reactions. Endothermic
reaction heat is normally supplied by a heat source while exothermic reaction heat is
usually removed in the products and heat sinks. For both cases, the energy must balance.
perfectly across the reactor and the overall process.

Time is not a variable in steady state analysis. Rather, the steady state concept is used to
represent the average operation of a process for a period of elapsed time. For example, a
plant test is conducted for a period of 24 hours and the process inputs and outputs of
material and energy are recorded for that period of time. The steady state operation is
defined as the 24-hour test period. In similar fashion, a steady state operation may be
defined for the average operation of the plant for a longer period of time such as a month.
In :he petroleum industry: the steady state time is commonly expressed in terms of one
twenty-four hour day.

Regardless of the length of time chosen to define a steady state operation, it is likely that
the process deviated from the steady state during that time period. Deviations arc caused
le:. feed stock composition and rate changes, changes in specificati'ons and rates for
products, set point changes in the process because of minor upsets, and start-ups and
shut-downs for the process or individual unit operations within the process. Processes
may deviate greatly from steady state during start-ups and slrut-downs, and these time
peciods should never be used for steady state representation of the process.

S:eady state simulation is widely used for the design and analysis of chemical processes.
For design it is also necessary to consider maximum and minimum limits which may
ovcur during start-ups, shut-downs, and upset conditions for the process. Since each
s:eady state condition represents only one poinl in time, the evaluation of operating
cynamics requires a modified approach in which time is introduced as a variable. Time
dependent simulation is called dynamic simulation and is discussed briefly in the section
f:lllowing.

1.2
Dynamic Simulation

-:-he most basic form of dynamic si,~ulation is a series of <leady state simulations in
.,hich a process variable or variables are changed with time. For each snapshot in time,
::oe steady state condition of perfect material and energy balance is maintained. This type
:)f dynamic model is useful for analysis of control schemes such as those used for
jislillation operations. However, this type of model cannot properly analyze the dynamic
?erformance of some unit operations such as compressors where surges of material are
?rocessed during start-up or upset conditions.
3
if: "Cht7pler 1
True dynamic simulation requires sophisticated, time dependent models for the unit
operations. The number of calculations r~uired for dynamic models is many ti~nes that
required for steady state models. Hlstoncally, the speed ar.d storage capaCIties for
computers have limited the use of dynamic simulation, particularly for modeling of large
processes. In past years, limited-scope dynamic modules were developed for use m plant
start-ups and shut-downs, process control, and operator training. .

Current advances in computer technology have made possible the consideration of


dynamic simulation models for large process flow sheets. It is probable that, in the
future, dynamic simulation models will find widespread use in operator training and
determination of .optimum set points for large chemical processes. Nevertheless, the
greater share of process modeling today is steady state simulation and this is the focus of
this book.

1.3
Steady State Simulation Program Features
Commercial simulation programs provide a common list of features: a pure component
data library, estimation procedures for non-library components, thermodynamic methods.
physical and transport properties, simulated laboratory tests, unit operation calculations,
special flow sheet building modules, and a user interface for program input and output.

All of the unit operation calculations are based On feed streams comprised of distinc:
chemical components, for which various thermophysical properties are available
Calculated results always include product streams comprised of the same chemical
components (or corresponding reaction-produced components); therefore, it is convenient
10 store calculated results from the unit operations as streams. A product stream from onc
unit operation may become a feed stream to another and so forth. In this fashion, the
process flow sheet is constructed using the streams as the connectors.

The calculation platform of most interest is the personal computer (PC), and all vendors
offer PC versions of their products. Ease of use is important for PC products, and all
commercial simulation programs provide a graphical interface, -in which process
information may be entered and retrieved via a process flow diagram (PFD). Portability
is an 'important feature for engineering programs, especially for engineers who commonly
"'isit operating plants in many locations. Laptop PC's have become very popular because
of their portability.

1.3.1
e Pure Component Data Library
)r
c .-\11 commercial simulators have large pure <:omponent libraries containing data for the
e "arious classes of chemical compounds encountered in chemical processing plants.
\' endors may develop these data for less common components, but most of the data
4 I."" ............................. __.__/ _.
~.
-
usually come from recognized reputable sources. Common sources for pure component
2
data include the PPDS' and DlPPR libraries. Some vendors also allow the licenser to
incorporate private technical libraries within their sc.ftware.

1.3.2
l'on-Library Components
No simulator is complete without procedures to estimate thermophysical properties fo.
non-library components. Open literature estimation procedures are commonly employed
in which component properties are related to chemical structurc.

For petroleum streams, structural data are not available for non-library components and
properties- must be estimated from such correlating parameters as normal boiling poir,t,
specific gravity, and molecular weight. The concept of pseudo-components is used,
where a pseudo-component represents a certain boiling point range of the feed stock.
Petroleum pseudo-components are discussed in more detail in Chapters 4 and 5.
Simulation programs lacking petroleum pseudo-.:omponent capabilities are not suited to
the modeling of the petroleum processes.

1.3.3
Thermodynamic Methods
II, Thermodynamic data include vapor-liquid equilibrium ratios (K values), enthalpies, and
entropies. These properties are necessary for the unit operation calculations, particularly
the first two. Entropies are used for isentropic calculations such as compression and
expansion. Calculation methods for K values include equations of state, liquid activity
c.oefficients, and empirical formulae.

The accuracy of an equation of state is improved by incorporation of tuning factors based


on pure component binary vapor-liquid equilibrium data. Liquid activity coefficients are
calculated with standard equation forms using pre-determined coefficients. These data
and other relevant parameters are kept in thermodynamic data banks in commercial
simulators. Many of the thermodynamic parameters are vendor-devcloped; however,
there are also recognized sources for data such as the DECHEMA' Chemistry Data
Series. The user may also supply thermodynamic parameters as program input. The
accuracy of the K values predicted by the various thermodynamic methods is largely
determined by the quality of the thermodynamic data bank intormation and user-supplied
parameters.

Enthalpies and entropies are commonly calculated using expressions derived from
equations of state that relate the enthalpy of the mixture to the cnthalpy of the mixture in
the ideal gas state. Ideal gas enthalpies are computed for each component and pseudo-
component using polynomial equations in temperature.
I 5

1.3.4
Physical and Transport Properties

It is useful to calculate physical and transport properties for the feed and product streams
in a simulation model. These properties may be calculated using the individual
component contributions, or determined based on the average properties for the stream
properties computed from individual component data include stream total flow in mole,
weight, and volume units, and stream density. Transport properties such as viscosities,
thermal conductivities, and liquid surface tension are commonly computed usmg the
principle of corresponding states.

1.3.5
Simulated Laboratory Tests
The specifications for petroleum products are based on standardized laboratory tests.
Most commercial simulators include methods to simulate these tests. Laboratory tests
include distillations, vapor pressures, {lash points, pour points, rreeze points, cetane
numbers, octane numbers, densities, and viscosities.

Accuracy of the simulated test depends on two factors: how well actual test data can be
correlated into a predictive equation, and how well the composition effect can be
represented with the components and pseudo-components used in the model. Some tests
such as octane, pour point, and viscosity nearly defy correlation because they are so
composition dependent. More discussion on laboratory tests is given in Chapter 3.
'. :ivity
1.3.6
.ased
Unit Operation Calculations

It is convenient in chemical engineering to divide processes into a series of calculation


steps called unit operations, which commonly appear in process after process. The
individual unit operations have common techniques and are based o~n the same scientific
principles Commercial simulators provide individual unit operations as building blocks
that may be linked together via the process streams to form the process flow sheet.

Cnit opera:ions include the following: vapor-liquid equilibrium separation, heat transfer,
tluid flow. reaction, and mass transfer operations such as distillation, absorption,
stripping, ditTusion, and adsorption. An additional subset of unit operations is available
for handling solids and inorganic processes; however, these operations are not nceded for
the petroleum processes and are omitted frorn discussion

The fundamental unit operation is vapor-liquid equilibrium separation (also known as


"flash" separation). K values are used in a calculation procedure to determine the vapor
and liquid ;Jortions of a mixture at a given temperature and pressure. One or two liquid

,.
6

phases are considered to be in equilibrium with one homogenous vapor phase. In plant
operations, a simple drum is used for flash separations, with the vapor leaving in an
overhead line and the liquid or liquids drawn out of the bottom of the drum. The flash
separation principle is used as a subset of nearly every other unit operation.

Heat transfer calculations include heat exchangers, furnaces, and coolers. Fluid flow
operations include pumps, compressors, pipes, and valves. A variety of reactor types
may be pro\~ded, including stoichiometric, equilibrium, kinetic, and Gibbs free energy
minimization.

Distillation and its subsets of absorption and stripping are the most important unit
operations in petroleum processes. Diffusion and adsorption seldom have application and
are omitted in the discussion below.

The distillation process consists of a vertical series of inter-linked flash separations, in


which the vapor product from one separation ascends to the next higher as a feed and the
liquid descends to the next lower as a feed. The separation steps are designated as
theoretical trays and the composite group of trays is called a columll. The vapor from the
top tray is condensed, and some of the liquid is returned to the top tray as reflux. Reflux
flows dO'Wll the column, wa,hing the heavier components down the column. Liquid from
the bottom of the column is warmed by a heat source (reboiler) and the resultant vapors
are returned to the bottom tray of the column as stripping vapor. The stripping vapor
flows upward through the column, carrying the lighter components in the feed up the
column.

Distillation calculations are based on steady state operation. At solution, every column
has a perfect mass balance for every component for every tray as well as for the entire
column. Likewise, there is a perfect energy balance for every tray and the entire column.
Finally, every tray is at vapor-Iiquid equilibrium and has both liquid and vapor products.
It is sometimes desirable to impose additional performance specifications on the solution,
related to the product qualities, quantities, and the column operating conditions.

Distillation calculations are iterative, starting from an assumed set of product flows and
tray temperatures. Several methods have been devised to solve the matrix describing the
various mathematical relationships for the column.

1.3.7
Special Flow Sheet Modules
Several auxiliary modules are used in process modeling. Stream mixers and splitters (or
tees) are used to combine and split flow sheet streams corresponding to stream junction
points in the process flow sheet.

Some processes have reG}'c1es, in which a unit operation product stream is returned to an
upstream operation for re-processing. The recycle stream will reach a constant

i
7

mposition, rate, temperature, and pressure in the steady state. To model the recycle
~culation, .the downstream product stream is directly substituted as a feed to the
upstream operation. This procedure is repeated until the recycle stream reaches the
steady state. M~st simulators have accelerator techmques for recycle calculations, In
which a new recycle stream composition is predicted, based on two or more previously
calculated compositions.

Other useful flow sheet modules include feed back and feed forward controllers.
Feedback controllers are used to adjust an upstream process variable such as temperature
to produce a desired downstream result such as a product quality. Feed forward
controllers are used to set downstream operating conditions based on calculated upstream
results.

All simulators have an empirical stream separation module, in which a feed stream is
separated into two streams using a defined set of individual component separation
factors. This module finds utility in short cut representation of auxiliary process flow
sheets within the main process flow sheet.

Another useful concept provided in many simulators is a user-defined calculation block


in which special calculations may be defined. The.se calculations may represent
proprietary technology or a unit operation not provided by the program vendor.

1.3.8
G ra phicaJ Interface

nn. The graphical capabilities of PC's are useful for simulation programs. The user may
;Is. build a PFD visually on the screen. This reduces errors in definition of the flow sheet and
is also a convenient means to provide the operating data for the individual unit
operations. The PFD may also be used to retrieve calculated results for specific unit
operations.
nd
he 1.4
Steady State Simulation Programs
O\'er one hund~ed and thirty programs are listed in the A.I.Ch.E. Software Directory'
Cinder the category "Process Design/Simulation" The following listed programs are
general process simulation programs with petroleum pseudo-component capabilities:
or
Program Name Program Vendor Vendor Location
~SPEN PLUS Apsen Technology Cambridge. MA, USA
':"H EA1CA D /J" Chemstations, Inc. Houston, TX, USA
DES/CS 1/ Windows Simulation Company Houston, TX, USA
HYS/M Hyprotech, Ltd. Calgary, Alberta, Canada
H),SYS Hyprotech. Ltd. Calgary, Alberta, Canada
o
---
Deerhaven Technical Software Burlington, MA, USA
PD-PLUS
Simulation Sciences, Inc. Brea, CA, USA
PROVISION
Bryan Research & Engineering Bryan, TX, USA
PROSIM
Notes: I) HYSYS is the future replacement for HYSIM. 11 has both steady slate and dynamic
simulation capabilities.

This list is not intended to be a complete list of every simulation program applicable to
petroleum processing nor is this book intended to be a treatise on the relative merits of
the ahove products. The reader is encouraged to cun;~ct snl[ware vendors dire:::l), fer
more information on specific products.

When presented in this book, examples and simulator specific information are limited to
the HYSIM, HYSYS, and PROVISION programs for which the author has extensive
experience. This is not meant to imply that other products cannot be used to produce
satisfactory results.

fP'
J
9

I PPDS (Physical Propeny Data Service) and the National Engineering Laboratory ,n
association with the Institute of Chemical Engineers, England.

2 DJPPR Data Compilation of Pure Compol/nd Properties, American Institute ',C

Chemical Engineers, 345 E. 47 St., New York, NY 10017.

3 DECHEMA , the German Society for Chemical Apparatus, Chemical Engineering, am'
Biotechnology.

4 1998 CEP Software Directory, American Institute of Chemical Engineers, 345 E. 47


St., New York, J'.,ry 10017 (January 1998).
-,--

Chapter 2
Composition of Petroleum Refinery Feed Stocks
d
"
I1
I
The primary raw material for all of the petroleum processes is crude .oil. Crude oil is a
naturally occurring liquid resource produced from wells drilled into the earth. The depth
of crude oil wells and methods used to produce the oil vary widely around the world.
T',,~ nature 2nd chemical composition of crude oil also vary widely, depending on the
geographical region from which it is produced. In fact, crude oil may vary widely in
composition within the same producing field.

It is possible to make some generalizations about the nature of crude oil. First, it is
primarily a mixture of compounds containing hydrogen and carbon (ilydrocarbons).
Additionally, sui fur, nitrogen, and some inorganic salts are also found in most crude oil
mixtures. According to Gary and Handwerk"', the elementary composition of crude oil
usually falls within the following ranges.
I"
n:
:i Element % by weight
I'
Carbon 84 - 87
Hydrogen Il - 14
':
"i
Sui fur 0-3
, ' Nitrogen 0-0.6
,"!

11'
I':
Crude oil is classified roughly according to the predominant family of hydrocarbons it
contains as paraffin base, naphthene base, aromatic base, or asphalt base. Crude oil bases
;.,i\
I vary greatly with geography. The refining scheme is dependent on the crude oil base,
I
The relative values for crude oils depend on the processing costs and the market values
for thc'associated products.
"f
,.:

Crude oil is produced in all corners of the globe. However, greater than fifty percent of
the world's known reserves are located in the geographical region known as the "Middle
East". For this reason, this region will continue to be a strategic focal point for the
!Ih I,!
nations of the world.
i:i
il1,1 2.1
il Crude Oil Properties
!

Crude oil is a very complex mixture of thousands of hydrocarbons. A.p.l. Project 6 has
succeeded in isolating over 16,000 distinct hydrocarbon compounds from a single sample
of Oklahoma crude oil. In general, such complete analyses are not conducted on crude
oils, and no attempt is made to analyze for pure components in crude oil except for the
low boiling point distilled components (or light ends). A number of simple tests are used
to evaluate crude oils as potential refinery feeds.

10
tu

.1
':haJ~ter2 11

I
These tests include. the following: :~
: 1

1) Gravity, APl

The density of petroleum oil is expressed in the United States as API gravity, where API
gravity is related to specific gravity as follows:

Degrees API = (141.5 / sp.gr.) - 131.5

The specific gravity or API gravity is relative to the density of water at 60 degrees F
tis (15.9 degrees C). The expression for API is non-linear, and specific gravities must be
s) .. used when calculating the gravity for blends. The API gravity is an inverse relationship 'I
oil when compared to the specific gravity, and a higher value indicates a less dense material.
oil It is also useful to note as a reference point that the API gravity of water is 10.0. Crude
oil API gravities vary widely with the crude base, from heavy Venezuelan crude oils of
10.0 API to light paraffinic. condensates of 70 API. However, a large percentage of the
crude oils that are produced and refined have API gravities in the range 20 to 40 degrees
API. (0.825 to 0.934 specific gravity).

2) Boiling Point Range

The boiling point range for a crude oil is determined with a true boiling point distillation
test (TBP). This test is performed in an apparatus with sufficient fractionation to recover
it samples of the various products that can be distilled from the crude oil. Results for the
test are reported at one atmosphere of pressure. Unfortunately, it is not possible to
determine the complete boiling point range for most crude oils because the oils thermally
degrade above temperatures of approximately 650 degrees F (344 degrees C) and a
pressure of one atmosphere. Therefore, the pressure of the TBP still is gradually reduced
during a TBP distillation test to a low of approximately 40 mm of mercury (Hg) for the
f heaviest portion of the crude oil. A temperature of650 degrees F and pressure of 40 mm
Hg correspond to a temperature measurement at atmospheric pressure of 900 to 950
degrees F (483 to 510 degrees C) for most crude oils. According to Nelson" and others,
,he maximum boiling point for crude oil mixtures is greater than 1400 degrees F (760
degrees C).

3) Characterization Factor

The mo~t commonly used characterization factor is that proposed by Watson, Nelson, and
\lurphy'. It is defmed as:

K = [T 3 ]0)))/ sp. gr.

where T, is the mean average boiling point of the sample in degrees Rankine and sp. gr.
=
, 1.2 Composition of Refinery Feed Stocks i

11

i' is the specific gravity at 60 degrees F relative to water. This characterization factor has
been related to vis!A)sity, molecular weight. critical temperature, etc., so that almost any
., laboratory data may be used to estimate it. A factor of 10.0 or less indicates an aromatic
;
material and a factor of 15.0 indicates a paraffinic material. For most crude oil, the factor ;
is in the range 10.5 to 12.5. Note that this factor is a rough indicator of the hydrocarbon
class (or composition) for the crude oil. ~
:I
I'
4) Sulfur Content, \'.1 % i
.1
q
.:1
Sulfur content and API gravity have the greatest influence on the value of crude oil'. The
f
sulfur content of crude oil varies from a trace to greater than five weight percent. High tii
sulfur content crude oils are known as 'sour" crude oils and require more extensive
processing than low sulfur or "sweet" crude oi.!s. In general. the lower the API gravity
i
,.
I
for a crude oil the higher the sulfur content. However, there are exceptions to this rule,
with low API sweet crude oils and high API sour crude oils. The additional processing
i
!.r'I
!i
for sour crude oils involve hydrogen treating processes to convert the sulfur to H 2 S that i
'[ can be removed.
i
, f
5) Carbon Residue, \\1 % @
I This property is determined by destructively distilling a sample to elemental carbon Q
(coke) in the absence of air. It is a measure of the asphalt content in the crude oil and the
quantity of the lubricating oil portion that may be recovered as product. It is also used to i
determine the yields from coIcing processes and as a measure of the coke deposited on the
catalyst for catalytic cracking processes. In general, the higher the carbon residue for a
Ii
crude oil, the lower its value as a refinery feed stock. @
6) Salt Content. pounds/IOOO barrels I
All crude oil contains some inorganic salts, generally in the form of chlorides. If the salt
t;
content exceeds 10 pounds /1000 barrels of crude oil it is necessary to remove the salts @i
?:
prior to distillation of the crude oil to reduce corrosion in the crude distillation column
and its overhead condensers.
,"
7) Metals, parts/ million (ppm) by weight

Numerous metals occur in crude oil, with the most common being nickel and vanadium.
Metals tend to concentrate in the heavier fractions of the crude oil where they act as
poisons for the catalytic and hydrogen cracking processes. Other metals include arsenic,
,
f!I

copper, iron, and zinc.

8) Nitrogen Content, ,,1 %

Nitrogen compounds in crude oil reduce the activity of cracking catalysts. Most of the
nitrogen in crude oil is contained in the highest boiling fractions. High nitrogen content
crude oil may require special processing to remove the nitrogen.
e
c;---
p,

lJ

. 9) pour point, degrees F or degrees C

pour point is a measure of the paraffinicity or waxiness of a crude oiL A waxy crude oil
has a high pour point; that is, it congeals at a temperature higher than room temperature.
Conversely, a low pour point indicates an absence of paraffins and! or a presence of
aromatic compounds which tend to lower the pour point.

All of the above mentioned properties are indicators of the composition for a crude oil.
As previously stated, a true component breakdown is not USll:lUy determined for most
clude oil samples except for the low boiling portion. This portion includes pentanes and
other light components with normal boiling points below 100 degrees _F (38 degrees C).
For somc iight crude oils and condensates, a complete chemical breakdown can be
determined through the light naphtha portion (nomlal boiling point 200 degrees F) with
chromatography. but such data are not typically available for most crude oil samples.

2.2
Crude Oil Composition
Three general classes of hydrocarbons arc present in crude oil: paraffins, naphthenes, and
aromatics. Significant quantities of olefins do not naturaUy occur in petroleum. In oil I
refineries olefins are created in the cracking processes. Paraftins in crude oil range in
boiling point from methane to compounds with boiling points exceeding 1000 degrees F
(538 degrees C) Naphthenes have at least one saturated ring and range from
cyc!opentane through complicated multiple condensed-ring compounds. Aromatics have
al least one unsaturated ring and range from benzene through multiple condensed-ring
slructures with 56 carbon atoms or marc. As long side chains are added to ring
compound s they become more paraffinic in their properties and behavior. This makes it
dlfllcult to classify most crude oils as one particular class of hydrocarbons.

Asphalt content of crude oil is directly related to the concentration of aromatic


compounds and asphaltenes in the heaviest portion. While there are generalizations
useful for predicting asphalt production from crude oil, it is necessary to verify the
quaJit\' and quamity of asphalt that can be produced from a given crude oil in the
ieboralOry For crude oils that do not yield specification grade asphalt products, it is
necess"ry to process the heaviest portion in another heavy oil process such as a
hvdrocracking. coking, or a modified FCe operation.

2.3
Crude Oil Assay Data
.-\ large quantity of crude oil assay data are available for the crude oils of the world.
Some of the data are company proprietary; however, many of the data are available in
Open literature. A typical assay contains the following information for the crude oil:
14 Composition of Refinery Feed Stocks

I) Whole crude oil average properties:

Gravity,. weight percent sulfur, weight percent nitrogen, pour point, Viscoslhes, metal
contents, weight percent carbon residue, Reid vapor pressure, salt content, flash point,
percent asphaltene, bottom sediment and water (B S & W), light hydrocarbon yields (er-
C,), and boiling point curve.

2) Fractional properties:

Boiling point or cIIl-poin! range and yield on crude, properties as shown above for whole
crude oils, research octanes for gasoline fractions, smoke and freeze points for kerosenes,
naphthene and aromatic contents for reforming stock, and cetane number for diesel fuels.

It is important to note that crude oil assay data change over time for any crude oil. This is.
caused by two factors. First, the crude oil itself changes in composition over time as it is
produced from a given well. Secondly, a crude oil sample represents a mixture of the
.'1 crude oil produced in many wells and possibly many crude oil fields. Therefore, as new
wells and fields are brought on line, the composition of the mixture changes. For this
'/
! reason it is good practice to request a confirming sample for a cmde oil mixture being
used in " process design. A genel~l rule is to be wary of crude oil assays that are more
than two years old when accurate simulation work is required.

2.4
Crude Oil Blending

Many refineries process more than one crude oil. The individual crude oils may be
transported to the reflOery via trucks, pipelines, and ships. Since most refineries do not
ha ve sufficient cmde oil storage to isolate the variQus crude oils as they are received, the
crude oil in the storage tanks is a mixture of the crude oils received by the refinery. The
net result is that the crude oil mixture processed in the crude oil distillation unit varies as
the crude charge tank mixture changes.

This presents some problems for test runs conducted over short. time periods. The
volumes of the individual crude oils received by the refinery are available from the
refinery accounting system. However, for refineries that process mUltiple crude oils, it is
highly unlikely that the monthly average crude oil mixture from accounting data is an
accurate representation of the crude oil ruixture that was processed during the test run.
Choosing data for a longer time period, such as two to four weeks, is helpful in damping
variations in crude oil distillation yields caused by day to day t1uctuations in the crude oil
miXture.

'em

.. ',h'

15

,
I
James H. Gary and Glenn E. Handwerk, Petroleum Refilling Technology alld
Economics, 3rd edition, Marcel Dekker, Inc., New York, (1994), p. 23.

6. W. L. Nelson, Oil & GasJ., p.125,126, (March 25,1968).

7. Characterization of Petroleum Fractions, !1Id. EIIg. Chem., 27, 1460 (1935).

8. lames H. Gary and Glenn E. Handwerk, Petroleum Refining Technology and


Economics, 3rd edition, Marcel Dekker, Inc., New York, (1994), p. 25.
I,
j!
;
Chapter 3
Laboratory Testing of Petroleum Streams

I Because they are derived from crude oil, most petroleum streams consist of a continuum
of components from various hydrocarbon classes, A component by component analysis
is neither practical nor cost-effecJive and is rarely performed in the laboratory,
1\!-, \10reover, such analyses are nGt usually necessary since the qualities (compositions) of
Lt
I; the intermediate and tlnal products are controlled to meet simple laboratory tests. These
!
tests are designed to be quick, inexpensive, and repeatable within a reasonable accuracy,
,i~.
i'

In general, specifications for petroleum products allow a range of acceptable test results,
For example, the ASTM D86 end point for a gasoline blend must be less than or equal to
432 degrees F (223 degrees C), Thus, within reason, and assuming that the other test
specifications can be satisfactorily met, there is a range of end point test results that
;1
satisfy this specification,
:i!
i,1
11 Inspection of laboratory test results for streams in a petroleum process show that the test
results vary with time within some acceptable range, In fact, it is not unusual to see
variances in ASTM D86 temperature points of \0 to 20 degrees F (5,6 to 11 degrees Cl,
'I These variances are caused by changes in the process feed stock, set points, dC .
.,
11
!
When developing steady state simulation models, it is important to remember that the
laboratory test results for process streams can vary somewhat. It may not be possible or
"i
desirable to precisely match one particular set of test results for a given process stream
because of real time variations in the process and the accuracy and repeatability inherent
in the laboratory tests, In representing the steady state operation, it is often more realistic
to look at average test resuits for a given time period instead of single samples.

3.1
True Boiling Point Distillation (TBP)
The TBP distillation is the best representation of the true composition for a petroleum
stream. Cnfonunately, the time and expense required for this test restricts its use to crude
oil samples. Simpler, less costly tests are used for control-of the refining processes,

There are no standard test procedures for TBP distillations, The U.s Bureau of Mines
Hempel method and the ASTM D-285 test procedure are most commonly used,
According to Nelson', any equipment that accomplishes a good degree of fractionation is
termed ",rue-bailing-point" equipment. Gary and Handwerk 'o state thzt there is a trend
toward using a 155 distillation (ASTM D-2892) instead of the TBP. This method is
conducted using 15 theoretical stages and a still retlux ratio of 5: L

Because the TB? distillation tends to separate the individual mixture components
relati,ely sharply in order of boiling point, it is a good approximation of the separation
that ma\ be expected in an actual distillation column, Products are collected and

16

. , t:
r 1-
17

from the TBP still that correspond to the boiling point ranges for the desired
Additional tests are performed on these fractional products to determine the
expected qualities for the products. True boiling point temperatures are always reported
at a pressure 0(760 mm Hg (one atmosphere).

Petrolcum oils begin to thermally decompose or crack at a temperature of approximately


6~O degrecs F (344 degrees C) at one atmosphere. Therefore, the pressure of the TBP
stili is gradually reduced as this temperature is approached to avoid cracking the sample
and distorting measurement of the true components in the oil. For many TBP
apparatuses, the minimum pressure obtainable is 40 mm of Hg. The highest temperature
that can be measured at this pressure for most crude oils is in the range of 925 to 975
degrees r ~496 to 526 degrees C) when corrected to a pressure base of one atmosphere.

Because of the laboratory time required and the subsequent high cost for TBP
distillations, this test is often approximated using correlations that relate the TBP
temperatures to temperatures measured by other types of laboratory distillation stills.

3.2
ASTM D86 Distillation
The ASTM 086 distillation is the most common laboratory distillation used by petroleum
refiners. It has been widely used for process unit control and finished product
specifications. Application of this test is limited to the temperature at which the oil
begins to decompose or crack. When the cracking temperature is reached, the
temperature of the vapors from the still no longer increase since light cracked products
begin exiting the still. As previously mentioned, the approximate temperature at which
p(,troleum oils begin to crack is 650 degrees F (344 degrees C) at one atmosphere. The
exact cracking tempe rature for an oil sample depends On its chemical composition.
Paraffin base oils crack at lower temperatures than aromatic base oils, causing variances
in the cracking temperature threshold.

The ASTM 086 distillation is a non-fractionating distillation that is run at laboratory


room temperature and pressure. Temperatures are reported at a preSSUFe base of 760 mm
\
Hg For high altiwde laboratories the barometric pressure corrections to the observed \
:cmpcratures are significant and must not be ignored. Table 3.1" presents temperature
corrections for various laboratory barometric pressures.

The 086 distillation was originally called the Engler distillation since a simple Engler
distillation flask is used. All distilled vapors are removed from the still and condensed,
?-od no liquid reflux is returned to the flask. The condenser tube is cooled in an ice water '\
'oath and the test procedure" specifies the condensing temperature shall be maintained I
between 32 and 40 degrees F (0 to 4.5 degrees C). The light components that boil at
temperatures lower than the condensing temperature are lost from the distilled product.

18 LaDOralory 1e:)""g UJ 1 ~"vua.,,. ...IU "' ....... .,

Table 3.1
Temperature Corrections for Barometric Pressure"

Laboratory Pressure, mm Hg
Observed 572 597 622 648 673 698 724
Temp, F
50 12 10 8 7 5 4 2
100 13 II 9 8 6 4 2
150 14 12 10 8 6. 4 3
200 15 13 11 9 7 5 3
250 16 14 12 10 7 5 3
300 17 15 \3 10 8 6- - "
~

350 18 16 \3 11 8 6 4
400 19 17 14 12 9 6 4
450 21 18 15 12 9 7 4
500 22 19 16 13 10 7 4
550 23 20 17 14 II 7 4
600 24 21 18 14 II 8 5
650 25 22 18 15 12 8 5
700 26 :3 19 16 12 9 5

For use with ASTM D86 Distillations ..


Temperature corrections are in degrees Fahrenheit.

One hundred milliliters of sample are distilled and the vapor temperature versus volume
reco'-ered is recorded. The initial boiling pOil1l is defmed as the temperature at which the

!
I,11
first drop of liquid leaves the condenser tube. Thejina! boiling point or "end point" is the
highest temperature recorded during the test. The total volume of the distillate is
recorded as the recovery. Any liquid left in the still after the end point temperatur.e is
recorded is cooled and measured as the residue. The difference between 100 milliliters
P and the sum of the recovery and the residue is recorded as the loss. Repeatability of the
i
test is purported to be plus or minus 6 degrees F (3.3 degrees C) for the initial boiling
r
!
point and end point. Intermediate distillation points are reproducible within 2 m!. of
distiliate which corresponds to six to seven degrees F (3.3 to 3.9 degrees C).

3.3
Ii ASTM D1160 Distillation
The ASTM D 1160 laboratory distillation" is designed for high boiling samples in which
,i there is signifIcant cracking at atmospheric laboratory pressures. Typical samples for
which D 1160 distillations are useful are heavy heating oils, cracker gas oil feeds, and
residual oils. The test is similar la the ASTM D86 method with the notable exception
tha' the sample is distilled at a reduced pressure to inhibit cracking. The distillation

.,,). '-:,.
19

most commonly selected for ASTM 01160 lests is 10 mm Hg. All observed
pressure corrected to a basis of 760 mm Hg for reporting

AI 10 mm Hg, petroleum stocks can be distilled to a maximum boiling point temperature


of 950 to 1000 degrees F (510 to 538 degrees C) as reported on a 760 mm Hg basis.
Lower pressures are sometimes used to extend this boiling point range for residual stocks.
The reduced pressure used for 01160 distillations produces a separation of components
that is more ideal than that for 086 distillations. In fact, the 01160 method closely
approximates the TBP method, and the temperatures recorded for 50 percent distilled and
higher are assumed to be identical to the corresponding TBP temperatures. The 0.11.60
. method is sometimes used to ex"tend the TBP distillation curve for mixtures contaIning
!Jigh boiling materials, such as crude oils.

3.4
API Gravity
This property has been previously discussed. It is determined with a hydrometer and
corrected and reported at a basis 0[60 degrees F (15.9 degrees C).

3.5
Reid Vapor Pressure (R.V.P.)
The Reid vapor pressure test" is used to measure the front-end volatility of products in
the gasoline through heavy reforming naphtha boiling point range. Iw;orrelates.well with
tll!l. normal butane content _of t~!!!!l.P-.L~..J!ng..L~fi.!te(uyp.icall-adjust the Reid vapor
pressure of gasoline blends by adding or removi~,...butane. According to
NeiSoit-':"for gasol1rieliiilieRVP:'rangeo{Sio"TLi psi., the percentage of butanes in the
stream is approximately the same as the. R. V.P. The Reid vapor pressure is always
reported in absolute pressure units of psi, kpa, bar, etc. A modified Reid vapor pressure
test is also used to measure the vapor pressure of crude oils.

In the test procedure for gasolines and naphthas, one part of chi lIed~liquid sample at 3G
degrees F(2.6 degrees C) is combined with four parts laboratory air at 70 degrees F (21.4
degree9-C) in a bomb that has a pressure gauge attached to the lid. The bomb is placed in
a constant temperature bath at lOO degrees F (37.8 degrees Cl and when the pressure
gauge reaches a constant value this reading is recorded as the Reid vapor pressure. The
rcpeatability of the test is somewhat less than 0.5 psi.

The Reid vapor pressure is nearly the same as the true (ac/ua!) vapor pressure for
gasoline streams as shown in data gathered by Nelson" and reported in Table 3.2 below.
The largest deviations occur for the samples at the highest vapor pressures. The accuracy
of this test is highly dependent on proper sample handling since the major contributors to
the Reid vapor pressure boil below room temperature.
r

I' 20

Table 3.2
Relationship between the True and Reid Vapor Pressure
for Miscellaneous Volatile Products"

Chromatographic Simulated Distillations


I Gas chromatography procedures have been developed to predict the boiling point
distribution fOT a petroleum stock that corresponds to the distribution determined with the
more lengthy TBP distillation method. There are four standard tests currently in use by
refinery test laboratories: D3710, D2887, D2887 extended, and HTSD. They are
summarized in Table 3.3 below.

The most commonly used method" is as set forth in ASTM Standard D ~2887-73. This
of
method is limited to petroleum fractions with a final boiling point 1000 degrees F (538
degrees Cl or lower. The sample must also have a boiling point range of no less than lOO
degrees F (55 degrees C). Carbon disulfide is used for the carrier gas in this procedure.
Equipment used for D2887 simulated distillations (sim-dists) has been highly automated. -~
3 21

Table 3.3
Simulated Distillation Procedures

MethOd Application Standard Rang.e Report Basis


03710 gasolines, naphthas CS-C1s < 500 F volume %
D2887 cycle oils, gas oils Cs-C <1015 F weight %
D2887-ext heavy gas oil, crude C5-C6 0 <1140 F weight %
HTSD heavy gas oil, crude C~-CI20 <1382 F weight %

Note: The standard is a mixture of normal paraffins with carbon number ranges as shown.

All of the methods work in similar fashion. The chromatographic column is first
calibrated with a standard mixture of normal paraffin hydrocarbons. A calibration curve
of retention time in the column versus normal boiling point is developed for the normal
paraffin standard by progressively increasing the column temperature and recording the
areas of the individual components at timed intervals. The sample in question is next
introduced into the column and the retention times and the areas of the ~ample
components are recorded. The components in the sample are then assigned boiling points
by using the calibration curve of retention time versus boiling point developed for the
normal paraffin standard.

Crude oils and heavy residues have such high boiling points that the column temperature
cannot be increased enough to recover the highest boiling fractions. Therefore, the total
area of the sample is not known and the boiling point curve for the sample cannot be
determined accurately for these streams.

High temperature simulated distillation, HTSD, is a modification" to the D2887


procedure which extends the boiling range distribution of hydrocarbons to a final boiling
point of approximately 1382 degrees F (750 degrees C). A careful choice of
chromatographic conditions is used to cause the high boiling components to be eluted
from the column some 500 to 600 degrees F (260 to 316 degrees C) below their normal
boiling points. This modification ~hows great potential for analysis Of heavy petroleum
residues.

With good laboratory technique, reproducibility of boiling point curves using


c~romatography is much better than that for conventional laboratory distillations. This
Dlakes the test desirable for process control. . As the technique is further developed and
Improved it most likely will replace the laboratory distillations, in particular, the TBP
distillation.

The method has been found to have some limitations for mixtures containing aromatic
compounds boiling higher than the gasoline range. These aromati~ compounds have
lower retention times than the normal paraffins of similar boiling points. Thus, the
boiling point curve predicted using th!!.paraffin standard calibration curve is lower than
,
I
22 Laboratory Testing oJPetroleum ;:'/feu",.

the actual boiling point curve for the sample. This may be overcome by developing
.,i
aromatic correction factors for the simulated distillation remperatures. Because the
correction factors depend on the relative quantities of the aromatic compounds in the
sample, multiple sets of correction factors are required to accurately represent the various
refinery samples containing high boiling aromatic compounds.

3.7
Flash Point
The flash point test determines the temperature at which the vapors from a petroleum oil
will ignite or "flash". Two basic procedures are used to detennine the flash point: the
. Cleveland open Clip method (ASTM D92), and the Penskey Martens (ASTM D93) and
the Tag (ASTM D53) closed ClIp methods.

To detennine the flash point, a sample is heated at a specified rate and an open flame
introduced into the emitted vapors at specified time intervals. The .temperature at which
the vapors ignite is recorded as the flash point. The open cup method is often used
because of its simpl icity. Below flash points of 51 0 degrees F (266 degrees C), the open
cup flash point is approximately 10 degrees F (5.6 degrees C) higher than the closed CLlp
flash point for the same sample. The open cup method heats the oil at a rate of 10
degrees F (5.6 degrees C) per minute with the test flame applied at 30 second intervals.
Therefore, the best accuracy that could be expected from this method is plus or minus 5
degrees F (2.8 degrees C). The closed cup tester heats the oil at a rate of 1.8 degrees F
per minute and is the more precise of the two methods.

3.8 Pour Point


j
The pour point test (ASTM D97) is useful in determining the waxiness of a petroleum oil.
A sample of oil is first heated to 115 degrees F (46.4 degrees C) to ensure that all wax is I
in solution. It is then cooled to 90 degrees F (32.6 degrees C). The sample is now placed I
in a cooling bath that is maintained from IS to 30 degrees F (8.3 - 16.7 degrees C) below -~

the pour point of the oil. The test jar containing the oil is removed from the bath at 5
degree F (2.8 degree C) intervals and tilted to determine if the oil will flow. If no
movement is detected for 5 seconds the solid point has been reached. The pour point is
defined as the temperature 5 degrees F (2.8 degrees C) above the solid point.

The same procedure is used to determine the cloud point of a petroleum oil. The cloud
point is defined as the temperature at which a distinct cloudiness or formation of crystals
appears in the bottom of the test jar. The cloud point is typically about 5 degrees F (2.8
degrees C) higher than the pour point.

--'----~----
23

The' viscosity of an oil is its internal resistance to flow and a measure of its usefulness as
a lubricating substance. The Saybolt Universal viscosity test (ASTM 088) is the most
common method used by refiners. The time in seconds is measured for a sample of 60 cc
of oil to flow from a container through a calibrated orifice at a prescribed temperature.
The usual test temperatures are 100 and 210 degrees F (37.8 and 99.2 degrees C).

Saybolt viscosities are reported as seconds. The Saybolt Furol viscosity test (ASTM
088) is a similar test for heavy fuel oils and uses a larger orifice. Saybolt Furol
viscosities are reported at 122 and 210 degrees F (50.3 and 99.2 degrees C). Tables are
used to convert Saybolt viscosities to kinematic viscosities.

Viscosities at other temperatures may be determined with ASTM viscosity paper,. on


which a straight line is used to connect two known viscosity! temperature points. Values
for intermediate temperatures are read from this line.

3.10
Octanes
The octane test is used to measure the knocking characteristics of a fuel in a laboratory
gasoline engine. The engine is calibrated by measuring the knocking value for a standard
material, 2-2-4 trimethyl pentane (2241MP). By definition, an octane number of 100.0 is
assigned to 224TMP. The knocking value of the test sample is next determined and
compared to the knocking value for the 224TMP standard to determine its octane.

Two octane tests are run for gasoline: the Research method (F-I) and the Molor method
(F-2). F-I octanes are higher than F-2 octanes because of test engine Oifferences. The
F-2 octane is a better measure of the performance of the gasoline in a commercial
automobile engine because the conditions of the F-2 test more closely approximate actual
motoring conditions. Historically, gasoline was sold by the highet:. F-I value. The
current trend is to advertise the average octane from the two tests, i.e., (R + M) !2.

3.11
Cetane
The cetane number is used to measure the performance of a fuel in a diesel engine.
Historically it was determined in a laboratory engine (ASTM engine test 0613), but
today it is usualiy calculated with a formula that relates cetane number, API gravity, and
. ASTM 086 50 percent distilled. An extensive evaluation of methods to compute cetane
has been published by Collins and Unzelman" orthe Ethyl Corporation.
24 Laboratory Testing of PetrQleum Streams

In summary, all of the above mentioned laboratory tests are used to evaluate the qualities
of feed stocks and products from the petroleum processes. They are. important in
simulation since they can be used to define petroleum pseudo-components to represent
the streams for the unit operation calculations. This concept is discussed further in
Chapter 4. .

References:

9. W. L Nelson, Petroleum Refille/)' Engineering, 4th edition, McGraw-Hill Book


Company, Inc.,. New York, (1958), p. 95.

10. James H. Gary and Glenn E. Handwerk, Petroleum Refining Technology and
Economics, 3rd edition, Marcel Dekker, Inc.,. New York, (1994), p.27.
/.
i
11. G. L. Kaes from K M. Buster, Personal Communication, (1964).

12. American Society for Testing and Materials, Part 23, Method D86-IP 123,
Philadelphia, P A (1982)
,
13. Ibid, Part 23. M(:'Lod D1160.
,I
I 14. Ibid, Method D323-56.

15. W. L Nelson, Petroleum Refinery ElIgineerillg, 4th edition, McGraw-Hill Book


Company, Inc., New York, (1958), p. 133.

16.lbld, p. 138

17. American Society for Testing and Materials, Part 24, Method D2Sg7-73,
Philadelphia, PA (1982).

I g. Villalanti, D.C., Jansen and P.Colle, "Hydrocarbon Characterization by High


Temperature Simulated Distillation", 1995 Al.Ch.E. Spring Nationa~Meeting, Houston,
Texas, (March 19-23, 1995).

:~ 19. Collins. 1. ~l. and Unzelman, G. H., "Better Cetane Prediction Equations Developed",
ij
Oil & Gas./., p. 148160, (Jur.e 7,1982).

11
.1

.. ----. ,~, "


", ........ _pter 4 .
Developing Petroleum Pseudo-components

For the unit operation calculations, it is necessary to rePresent all process streams with
discreet components for which thermophysical properties may be defined. Since most of
the actual components are unknown for petroleum streams, petroleum pseudo-
components are developed to represent the unknown components in these streams.
pseudo-components represent pre-defined boiling point ranges or cut-point ranges on the
TBP distillation curve for the stream being characterized. Each pseudo-component
corresponds to several unknown actual components.

Three correlating parameters are commonly used to estimate therrnophysical properties


for petroleum pseudo-components: normal boiling point, specific gravity, and molecular
weight. Open literature correlations el)able the prediction of any of these three
parameters from the othertwo. For a pseudo-component, these parameters are the weight
averaged values for the TBP cut-point range of the pseudo-component.

The compositions for all flow sheet streams are represented with act'Jal components and
pseudo-components. Laboratory distillations and various other properties are predicted
for these streams from their composit ions. Properties highly influenced by chemical
class such as pour point are difficult to predict accurately with pseudo-components since
a pseudo-component may represent several actual components of more than one chemical
class.

4.1
Pseudo-component Normal Boiling Points
The first step in development of pseudo-components is definition of the pseudo-
component cut-point ranges on the stream TBP distillation curve. As mentioned
previously, TBP distillations are seldom' run in the laboratory because of the time
required and the associated high cost. Alternately, another type of laboratory distillation
is used and a correlation is used to convert the test data to the corresponding 760 mm Hg
TBP distillation.

The conversion step introduces another degree of uncertainty into the characterization of
petroleum streams since the distillation inter-conversion methods are based on a limited
number of samples of limited accuracy. However, it is the necessary first step when an
actual TBP distillation is unavailable

Pseudo-component cut-point ranges are next defined and applied to the actual or
predicted TBP distillation curve. The normal boiling point for each pseudo-component is
defined as the weight average temperature for its cut-point range.

25
26 Developing J'etroleum rseuao-cumJ1U"~"w

4.1.1
Conversion of D86 Distillations
The most widely accepted methods for conversion of D86 distillations to TBP
lO
distillations are derivatives of the Edmister and Pollock correlation. A revision of this
method was published by Edmister and Okamoto" in 1959 and is illustrated in Figure
4.1. This method consists of two graphs. The first graph relates the D86 50 % distilled
t~mperature to the TBP 50 % distilled temperature. The second graph ;s a family of
curves relating the D86 temperature slopes to the TBP temperature slopes for segments of
the distillation curve as follows: 0-10 %, 10-30 %,30-50 %,50-70 %,70-90 %, and 90-
100 % distilled. The method is illustrated in Table 4.1 below.

Table 4.1
Conversion ofD86 to Data with the Edmister and Okamoto Method (Figure 4.1)

Corresponding
D86 Temp. TBPTemp.
% Distilled D86, Dca F Diff., DegF Diff., Deg F TBP, DeQ F
0 107 40
0-10 32 57
10 I ~J
"Q 97
/0-30 43 68 . ,I
30 182 165 .~
30-50 58 77
50 240 242 Starting Point

50-70 60 76
70 300 318
70-90 65 75
90 365 393
90-100 60 65
lOO 425 458
<

No provision exists for conversion of other distilled percents, e.g., 5, 20, 40, 60, 80, and
95. Commercial simulators determine these points by quadratic interpolation of the
predicted TBP curve. Note that the Edmister and Okamoto method always predicts a
distillation curve with a positive slope. This correlation has found widespread acceptance
by petroleum refiners. American Petroleum Institute (API) Technical Data Books
published prior to 1987 present the Edmister, et. aI., method as Figure 3AL I.
27

Figure 4.1 .
Conversion of D86 Distillation to TBP Distillation
21
Method of Edmister and Okamoto

Figure 4.18: Volumetric slope conversions

Figure ".1A: 50% convers;on

160
1/ I#.
'" .. 160
rI
""
..
'"
TS? 50 % ro
140
l!:
[,1
TB?
minus t:1'
Temperature 100
08650%. !XI
Difference,
Deg F ~ DegF 80

60

40
19'$

" f-

ASTM D86 50 %, Degrees F o


o 20 (() 50 so 100 120 140 160 180

ASTM 086 Temperature DIfference, Oeg F

The 1987 API Technical Data Book introduced a new method for conversion of D86 to
TBP. This method was based on work done by Riazi and Daubert" and was based on a
different approach trom the earlier Edmister, et.a!' correlations. The following equation
form was used for all inter-conversions:

where: T = Absolute te'mperature, deg R


Sg = Stream average specific gravity, API
a,b,c = unique constants corresponding to 0, 10,30,50,70,90, and 95 % distilled
TBP. D86 = designate atmospheric TBP and ASTM D86 data, respectively

l'nfortunately, the Riazi and Daubert correlation resulted in prediction of TBP distillation
curves that were inconsistent for some cases. The point by point approach to inter-
conversion sometimes predicted TBP distillation curves with regions of negative slope
for petroleum streams with small boiling point ranges. Because of these anomalies, the
Riazi and Daubert method was not widely accepted by petroleum refiners and a new
study was commissioned for its replacement.

- --"-,.~.'-'
28 Developing Petroleum Pseudo-components
. n
In 1994 the results of the new study were published by Professor T. E. Oaubert . The
D86 and TBP data used by Riazi and Daubert were refit to different equation fonns. The
new correlation first converts the 086 50 % distilled temperature to the TBP 50 %
distilled temperature. Based on the 50 % distilled point, temperature increments for the
following ranges are added and subtracted to develop the complete TBP curve: 0-10 %,
10-30 %, 30-50 %, 50-70%, 70-90 %, and 90-100 % distilled. Observe that this is the
same approach taken by Edmister, et.al.

Professor Daubert reports that the new correlation is more accurate than the older
Edmister, et. aI., correlation. At this writing, there is insufficient industrial experience
with the new correlation to confirm this claim. However, it is likely that the new
correlation is a significant improvement over the 1987 Riazi and Daubert correlation.

All of the methods discussed above are in the open-literature and have been incorporated
'-finto commercial simulators/ The 1987 Riazi and Daubert method, however, shouldJ,Ol
_be used since it does not alw~ys 'produce satisfactOlY re~uits,: Furthermore, it can result in
distillation curves with negative slopes that are a physical impossibility.

4.1.1.1
D86 Cracking Corrections
!;
Figure 3Al.l of API Technical Data Books published prior to 1987 presents an equation
to correct observed ASlM D86 temperatures for cracking. The correction is applied to
ASTM D86 temperatures greater than 475 degrees F (246.4 degrees C) and is calculated
with the following equation:

log,o D = 0.00473 (T) - 1.587


i,
where:
D = correction to be added to observed D86 temperature, degrees F
T = observed 086 distillation temperature, degrees F.
t
"[,
Calculation of the cracking correction is illustrated in Table 4.2. Although the more
recent versions of the API Technical Data Book no longer include-this method, most
11
commercial simulators still make it available. However, this simple equation is a gross
I'
ill oversimplification for the cracking of petroleum stocks in which chemical class is the
i:
!i controlling factor. The author recommends that this cracking correction not be used. t\
better approach is to use distillation probability paper to adjust the portion of th~
distillation curve for which cracking is occurring.

ii11
29

Table 4.2
Cracking Corrections for Observed D86 Distillations:

Observed D86 Corrected D86


. Temperature, F Temperature, F
500 506
550 560
600 618
650 681
700 753

4.1.2
Conversion of D1l60 Distillations
21
The Edmister and Okamoto method is used to convert ASTM DI160 distillation data to
TBP distillation data. The method is given in Figure 4.2 and has a pressure base of 10
mm Hg for the DI160 distillation and/he predicted TBP distillation.

D 1160 data are normally reported by laboratories on a 760 mm Hg basis. Therefore, the
first step in using the Edmister and Okamoto method is conversion of the laboratory data
to a 10 mm Hg basis with a Cox chart. Note from Figure 4.2 that no correction is applied
to the D 1160 temperatures for 50 percent distilled and higher. Correction curves are
given to adjust the DI160 temperature differences for the segments 0-10 %,10-30 %, and
30-50 % distilled. The final step in application of this method is use of a Cox chart to
convert the predicted 10 mm Hg TBP curve to a 760 mm Hg TBP curve.

4.1.3
Conversion of Simulated Distillations
The D2887 simulated distillation is a relatively new test. ASTM Standard D 2887-73
procedure was first published in 1973. This procedure is applicable to petroleum'
fractions with final boiling points of 1000 degrees F (538 degrees C) or less and boiling
ranges of at least 100 degrees F (55 degrees C). This limits the usefulness of the test for
residual materials such as topped crude oil that r..ay have final boiling points in excess of
1600 degrees F (871 degrees C). As previousl\' mentioned in Section 3.6, the test has
been revised to accommodate higher boiling stocks.

The first method for conversion of D2887 distillation data to TBP data was published by
Riazi and Daubert". This method involves two conversion steps. First, the D2887 data
are converted to D86 data with the following equation:
30 Deve/oping Petroleum Pseudo-components

Figure 4.2
Conversion of D1160 10 mm Hg Distillation to TBP 10 mm Hg Distillation
Method of Edmister and Okamoto"
240

220 1/
::00
1/, ,
180
1/
lGO /
140
104( "AN 30-
,
% V
120 ~
/
/, V
(,f ~
100
/
:Y '"
70% N07 .so%

'l "Vv
80
01 %
/ '"
., GO I I ,
}1
!

40 I
20 !~
,, W
o 20 40 60 80 100 121:1 U.O 160 180 200 220 240

ASTM 01160 TEMPERATURE DIFFERENCE, DEG F

.1

F=
wher.e .0
. 009524 ( T 02881 10%)
0
0.0'''' ( T
0211:87
50";')
0
0.6147

a, b, C = Constants for 086 0, 10, 30, 50, 70, 90, and 100 % distilled.
D86, D2887 = designate ASTM 086 and ASTM 02887 report ea temperatures
The second step is conversion of the predicted 086 temperatures to TBP temperatures
with the 1987 Riazi and Oaubert correlation discussed in Section 4. I. I.

The Riazi and Oaubert procedure has been made available in commercial simulators.
However, results are very poor because of the inherent inconsistencies in the approach
used for both the 086 and TBP temperature conversions, and the compounding of
inaccuracies by the two step conversion procedure. The conversion equations shown
above are also based on a limited sample base with the highest boiling point being 762
degrees F (406 C). Because of these problems and limitations, this conversion method is
not recommended and should lIot be used.

----- ..

4
4 31

As a part of the study to replace the Riazi and Oaubert inter-conversions, Oaubert'" also
efit. the 02887 distillation data to equations similar to the Edmister, et. al. correlations.
~ single conversion step is used in this latest procedure to predict the TBP temperatures
from the 02887 temperatures. In this procedure, the TBP 50 volume % distilled
(Cl11perature is assumed to be equal to the 02887 50 weight % distilled temperature. A
1:1mily of curves is next used to predict the TBP temperature differences for 0-10, 10-30,
10-50, 50-70, 70-90, and 90-100 volume percents frolll the corresponding D2887
;cmperaturc differences for 0-10, 10-30, 30-50, 50-70, 70-90, and 90-100 weight
percents.

The revised procedure published by Oaubert is an improvement from the earlier Riazi
and Daubert method. There is little industrial experience with this method to date, and it
is recommended that all predicted results from this method be carefully examined for
reasonableness.

As has been discussed in Seciion 3.6, simulated distillations are based on normal paraffin
boiling points and become inaccurate for streams containing appreciable coments of
aromatic compounds boiling above 400 degrees F (204.8 degrees C). Because of this
characteristic, it is not likely that a single correlation can ever be developed to accurately
predict TBP distillations from simulated distillations. Rather, the more accurate approach
is to develop individual conversion methods for the various types of refinery streams with
high aromatic contents, i,e., FCC slurry oil, coker gas oil, asphaltic crude oil, etc.

The following approach is recommended when using commercial simulators. Enter the
simulated distillation as if it were a TBP distillation to prevent the simulator from using
an inaccurate general conversion method. Note that the 02887, 02887 extended, and
I!TSO are entered on a mass basis; the 03710 is supplied on a volume basis. l\10dify the
T13P as needed to account for the aromatic content of the stream. The aromatic boiling
point correction may be estimated by comparison of the simulated distillation
(emperatures to another laboratory distillation such as the 01160. If no other laboratory
distillations are available, distillation probability paper may be used for a "cut and try"
approach until the model produces satisfactory temperatures for the products that colllain
the heavy aromatic compounds.

4.1.4
Selection ofTBP Cut-point Ranges
T13P cut-point ranges are used to define the pseudo-components, with the average
. temperature of tile cut-point range defined as the pseudo-component normal boiling point
(NBP). The number of cut-point ranges (or cuts) used to define the true boiling point
curve for a petroleum stock is somewhat arbitrary. Using a large number of cuts is not
generally justified in consideration of the accuracy ofa TBP boiling curve that is derived
762 from an ASTM laboratory distillation of limited accuracy. On the other hand, using too
od is few cuts results in a model that does not predict a continuous, smooth distillation for the
process streams such as occurs in a typical refinery distillation operation.
FT

32- uevelopmg Petroleum rseuao-compu"""'''

The following cut-point ranges are reasonable for most refining problems and are used as
defaults in many commercial simulators:

TBP TBP
Range, Range, Number of cuts
DegF DegC
--------
< 100 < 37.S Use actual components (pentanes and lighter)
100-S00 37.S-427 28
800-1200 427-649 8
1200-1600 649-871 4

The final selection of cut-point ranges for a model depends on the distributed components
in the fractionation zones. This concept will be further discussed in Chapter 7. Figure
4.3 illustrates selection of cut-point ranges for a petroleum stock.

Figure 4.3
Definition of TBP Cut-point Ranges for Petroleum Stock
4
Atmospheric TBP Distillation Curve
4
..!

x =pseudo-component average normal l


-
(/)

c
Q)
c
boiling pOInt (NBP)
4
o
a. o =Defined Component NBP .~
E .]
u. o
o 4
4
I .~

1
f t,,
~
!,

o
Liquid Volume %
100 t

I
'!hoJ'JIer 4 33

4.2 .
Development of Pseudo-component Gravities
Definition of the cut-point ranges establishes the normal boil ing points (NBPs) and
corresponding liquid volume flows for the pseudo-components. The next step is
determination of the pseudo-component gravities to establish the corresponding mass
flows. The minimum information required in this step is the average stream density for
the stream being characterized. When only the average stream density is supplied,
commercial simulators determine the pseudo-component gr~vities by assuming that the
Watsoll-Murphy K jactor is constant (or nearly constant) throughout the entire stream
boiling range. The Watson-Murphy K factor is computed for the stream average boiling
. point:
0)33
KO', = [ T ",.,l I sp.gr.."

where T So,,' sp.gr.", = stream average boiling point in degrees R and stream
specific gravity at 60 degrees F, respectively.

The stream average boiling point is defined by commercial simulators in a variety of


ways. Individual pseudo-component gravities are nex1 determined with this variation of
the formula above:
0.33)
sp.gr., = [ TB, 1 I K..,

.
where: K".. = stream average Watson-Murphy
.
K factor
TB, = pseudo-component average boiling point in degrees R

Specific gravities for the known components in the stream are extracted from the pure
component library. The stream gravity .curve must now be smoothed (or normalized)
such that the weight average sum of all of the component gravities in the stream equals
the supplied average stream gravity. Commercial simulators differ in the approach taken
in this step; however, they all agree in that the needed adjustment is done to the pseudo-
component gravities only. ~

The assumption of a constant Watson-Murphy characterization factor becomes less


accurate as the boiling point range for a stream increases.' For wide boiling streams such
as crude oil, the characterization factor for the lighter boil ing fractions is higher than the
_stream average value because of the higher paraffin content of these fractions.
Conversely, the characterization factor for the higher boiling fractions is lower than the
stream average because of the greater concentration of aromatic and asphaltene
compounds. Thus, a stream gravity curve developed with the stream average
characterization factor tends to have a slope that is too flat.
34 ueveloplng re,rUlt:U/1I . .>t;UUv-1,.;vmyv....... .....

I,fl.:,. Most commercial simulators provide an option by which additional points on the gravity
curve may be supplied. Such data are usually. available for crude oils, where several
fraction.s from the distillation test are rollected and analyzed. The gravities for these
fractions are entered at their mid-volume percents on the overall boiling curve to
establish a gravity curve for the stock. Normalization is still necessary for the pseudo-
component gravities derived from the supplied curve; however, the slope of the supplied
curve is held constant during the adjustment process. The resultant pseudo-component
gravities are a better representation of the chemical nature of the oil than those derived
with the constant characterization factor assumption.

Figure 4.4
Relationship of Pseudo-component Properties to the TBP Distillation Curve

Atmospheric TBP Distillation Curve

: ~
j~
o : pseudo-component NBP's
r/.~ !I I

"-,
~
is
I
I ........-.
f"f' ':
I
I
I
I
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I
I
U, ~ I I',
-I _~ I t' I I 11
~I """,,"-;'111 1 ),
, .... _ - . - I I I I I I I I
:J I ...... -. 1 I I I I I '1

i:
c I
~~~:!
---001"'--I,
i : : :
I I I I
I :
I
:
I
::
I I
.. ,.
;:: 1 ~7- I I I I I I I I I
III r
I I I I I I I I I I I
0.....111' : I I I : I I I I: I
~ It: I I I : : I : I :
': I : I I It: I I I
: I I:: I I t I ,
I

:
I
,
I

I
I
:', I
I I
I
I
I
I
I
I
I
I
I
I
1
I
I
I
I
I
'I
I
I
I

I
I
I
I
I
I
I
,
t
I
,, , , , , ,
,,, ,,, ,, ,,,
,, ,,
,, ,, ,,,
, ,,,
,, '.
,, ,,
,,, ,,, ,, ,,, , .Vf
, ,, .
,,, , ,,, ,
~
1 (' I I
"

...
I. I I

, , ~" :E
: .... y ," ,', I I "I I

, , of : ,
,, , ,,, ;=
lI'" ,, ~


I, 11::
I " ;''i''''~~l
,I
~_"'" t ,, ,,,
"5
0
: I : : : _~f -"
0
I I I I I !- ~'~ I

*
I
t
I
I
I
L ~
I *,01-.
t
I
I
:
I
:
I
'"
:: I >t-"'
I I
: If I I
I::
I 1

I
I

I
I I I I

o Liquid Volume % 100

=--"trr

t
t
';hiIplrer 4 35

4.3
Develop~ent of Pseudo-component Molecular Weights
Detennination of.the pseudo-component molecular weights is the final major step in
characterization of petroleum stocks. The relationship of the pseudo-component nonnal
boiling points, gravities, and molecular weights are shown in Figure 4.4 above. These
three correlating parameters allow the accurate prediction of other needed data for the
petroleum pseudo-components.

Molecular weiglit data are seldom available for petroleum stocks. Therefore, they are
predicted by commercial simulators based on the pseudo-component nonnal boiling
points and gravities. -Numerous open literature correlations have been .<:Ieveloped and
published since the 1930's that relate normal boiling point, gravity, and molecular weight.
Commercial simulators allow the user a variety of methods to predict molecular weight;
however, it is usually prudent to use the simulator default method since other
thermodynamic data may be tuned to the default molecular weights.

Similar to gravity data, most commercial simulators provide an option by which


molecular weight data may be supplied. The molecular weight for stream fractions are
entered at their mid-volume percents on the overall boiling curve to establish a molecular
weight curve for the stock. If the stream average molecular weight is also given, the
pseudo-component molecular weights are normalized such that the stream average is met.
The slope of the supplied curve is held constant during the adjustment process and the
resultant pseudo-component molecular weights will be a better representation of the
chemical nature of the stream than those derived with the open literature methods

A pseudo-component molecular weight predicted from only normal boiling point and
gravity is the least accurate of the three correlating parameters. First, any error in
predicting the gravity has a direct effect on its accuracy. Second, open literature methods
that relate normal boiling point, gravity,. and molecular weight have a bias toward
I
,"
1
paraffins. Thus, for highly aromatic materials, the methods may predict molecular
weights more representative of paraffins than aromatics. "ii
I
In fact, proprietary methods not available in the open literature ofte;introduce afourlh 1
1:1
correlating parameter such as the source of the petroleum stock; i.e., straight run,
catalytic cracker, coker, hydro cracker, etc. Since these methods are based on actual
experimental data they are more accurate than the open literature methods in commercial
it
'I
I,\.
simulators. Therefore they should be preferentially used when available. Commercial
simulators all have provision for the direct entry of the three correlating parameters for
petroleum pseudo-components.
36 Developing Petroleum Pseudo-componenls

4.4
Pseudo-component Enthalpies and Critical Properties
The open literature abounds with accurate methods for predicting enthalpies, entropies,
and critical properties for petroleum stocks from the three correlating parameters
previously discussed.

Enthalpies are typically computed with equations of state as deviations from the ideal gas
state. Thus, it is only necessary to predict the ideal gas enthalpy curves for the petroleum
pseudo-components to predict their enthalpies. Ideal gas enthalpies for hydrocarbons
correlate well to polynomiai expressions. Therefore, polynomial coefficients are derived
for standard ideal gas enthalpyequation forms using the pseudo-component normal
boiling points, gravities, and!or molecular weights.

Critical properties for petroleum pseudo-components also correlate well with normal
boiling point, gravity, and! or molecular weight and the open literature abounds with such
correlations. Plots of the simulator predicted pseudo-component properties should
a/ways be used to make certain that the entire boiling point range is renresented in a
reasonable fashion

Other pseudo-component properties required for thermodynamic calculations with


equations of state are discussed in Chapter 6.

References:

20 Edmister, W. C. and Pollock, D. H, "Phase Relations for Petroleum Fractions",


Chem. Engr. Prog. Vol. 44, p.905, (194S)

21 Edmister, W. C. and Okamoto, K. K., "Applied Hydrocarbon Thermodynamics-


Part 12: Equilibrium Flash Vaporization Correlations for Petroleum Fractions",
. Petroleum Refiner, Vol. 38, No. S, p. 117 (1959). '

22 Riazi, M. R. and Dauberl, T. E., "Analytical Correlations Inter-convert Distillation-


curve Types", Oil & Gas .I., p.50-S7, (August 25, 1986).

23 Daubert, T. E., "Petroleum Fraction Distillation Inter-conversions", Hydrocarbon


Processing, p. 75-78, (September 1994).

I - - >
i

i I
5
mitati~ns of Petroleum Pseudo-components

The concept of petroleum pseudo-components is necessary and useful for calculations


with petroleum feed stocks. However, the engineer must always remember that pseudo-
components are a gross oversimplification for the complex mixture of actual components
found in petroleum. A typical petroleum stream characterization uses 50 to 100 library
plus .pseudo-components to represent full boiling range crude oil. In reality, crude oil is a
continuous mixture of thousands of actual components.

Pseudo-components derived by commercial simulator programs do not represent the


composition effect very well because of limitations in the open literature correlations that
are used to predict the thermophysical properties. This limits the ability of commercial
simulators to predict accurate results for laboratory tests that are strongly influenced by
composition, e.g., pour point, viscosity, etc.

This chapter discusses the limitations inherent in petroleum pseudo-components


produced by commercial simulator programs. This does not invalidate the pseudo-
component approach to solving petroleum problems; however, these limitations must be
considered when interpreting the calculated results from commercial simulator programs.

5.1
Prediction of Laboratory Distillations
Commercial simulators use a discreet number of components and pseudo-components to
i
represent petroleum oil, which is a continuum of actual components. The selection of
TBP cut-point ranges for pseudo-components has been previously discussed in Section II
.1.1.4.
li
!i'
Calculations with the characterized feed stocks predict products with varying amounts of ii
these same components and pseudo-components. The laboratory distillations for
products are predicted by a procedure that is the exact reverse of the feed stock
characterization procedure.

For each flow sheet stream, the predicted TBP distillation is determined by volumetric
integration of its components in order of normal boiling point. The next step is to predict
the desired laboratory distillation; i.e., D86, D 1160, D2887, etc., using the conversion
relationships presented in Sections 4.1.1-4.1.3.

Some problems arise when predicting the TBP distillation by volumetric integration of
the normal boiling points for the stream components. This TBP is not smooth, and may
ha ve flat regions corresponding to blocks of discreet components and pseudo-
components. Therefore, it is necessary to smooth this rough curve to reproduce the
characteristic shape of an actual TBP distillation curve.

37
38 limitations ofpseudo-components (I
Prediction of the TBP initial and end point temperatures preseitt special problems. In the
real world, these points represent small quantities of light and heavy components. A
I
typical characterization uses cut-point ranges of25 to 100 degrees F (\3.9 to 55.6 degrees i
C) for the highest boiling fraction of the petroleum stock. The lowest boiling fraction is I I
represented by pure component boiling points and/ or pseudo-component cut-point ranges
of 25 degrees F (13.9 degrees C). Thus, the first and last component may represent
several percent of the distillation curve. For this reason, commercial simulators
tI
(
arbitrarily define the predicted TBP initial boiling point and end point temperatures as
those temperatures corresponding to 1.0 volume % and 98.0 volume % distilled, I I
respectively. These default percentages may be changed by the user, but this will have
little effect without corresponding changes in the pseudo-component cut-point ranges.

It is also noteworthy to remember that the distillation curve slopes for the initial and final
portions of all types of laboratOIY distillations are much steeper than those for the middle
portions. Therefore, the conversion correlations have higher errors when predicting the
initial and end points corresponding to the simulated TBP temperatures. This compounds
the problems caused by the discreet blocks of components, and the net result is that the
predicted initial und end points for laboratory distillations are not reliable.

Initial and end point temperatures are used in many petroleum product :;cciflcations.
However, for simulation purposes, it is better to estimate the corresponding 5 and 95
volume percent temperatures to use for the simulation specifications. It is doubtful that
commercial simulators can accurately predict the true magnitude of end point and initial
point temperature changes that occur in operating plants when productcut-points are
changed. If the predicted initial and end point temperatures are used for decision making,
the corresponding changes in the 5 and 9S volume percent temperatures should a/ways be
reviewed as a test of reasonableness.

5.2
Prediction of True Stream Composition
Two prOblems arise in prediction of the true stream composition: the cut-point ranges,
and inaccuracies in the open literature methods used to predict the pseudo-component
proper1ies. Unfortunately, these problems are additive. -

Obviously, the cut-point width has an important effect. Users of commercial simulation
programs usually do not specify the cut-point ranges and the default ranges are used in
the characterization process. Default cut-point ranges may vary from 25 to 100 degrees F
(13 9 - 55.6 degrees C). In terms ofactuai components, a cut-point range of25 degrees F
may represent many components of different chemical class and/ or isomer structure.
Table 5. I below illustrates tbe actual components that may be present in the cut-point
range of a pseUdo-component developed for Fee gasoline with a commercial simulator.

-----
. ----..--.
Chapter 5 39

Table 5.1
possible Actual Components in One
FCC Gasoline Pseudo-component

J'seudo-com ponent Properties:


Cut-point range on TBP: 150 - 175 degrees F
Average NBP, degrees F = 164
Average API Gravity = 63.4
Average Molecular Weight = 84.4

NBP, Grav., Mole F-1 Ht of formation.,


Pure Component Class deg F API Wt Octane btullb-mole
----------------- -.-------- --.---.-_.-
n-hexane paraffin 155.7 81.6 86.2 24.8 -71,900
2,2dimethylpentane paraffin 174.6 77.1 100.2 92.8 -88,500
methylcyclopentane naphthene 161.3 56.2 84.2 91.3 -45,900
I-hexene olefin 146.3 72.2 84.2 83.0 -17,900
I-M-cyclopentene olefin 158.4 48.7 82.1 >100
4-M-cyc1opentene olefin 167.4 48.8 82.1 >100
benzene (See note) aromatic 176.2 28.4 78.1 100 35,700

Note: benzene is likely present because of azeotroping.

Four distinct classes of component are represented by the one pseudo-component shown
above in Table 5.1. The average properties predicted by the simulator cannot possibly
represent the unique properties corresponding to each pure component. Thus, a property
such as F-I octane that is highly dependent on both component class and isomer structure
cannot possibly be predicted for the above pseudo-component with any measure or
accuracy.

Furthermore, the average pseudo-component properties predicted by a- simulator have a


definite paraffin bias. The open literature correlations used to predict pseudo-component
properties ha vc a bias toward paraffins since much of the data used in their development
are for paraffins. Therefore, as might be expected, prediction of pseudo-component
properties for streams rich in paraffins (such as straight run gasoline) will be more
accurate than those for streams rich in ring structures and unsaturated compounds.

5.3
Sim ulation of Refinery Reactors
This subject will be discussed in more detail later in this book. However, it is apparent
from the discussion in Section 5.2 that pseudo-components from commercial simulators
~
40 Limitations ofpseudo-components

cannot represent stream compositions accurately !n terms of unique classes and isomers
, "
, of hydrocarbons. The catalytic and thermal reactions that occur in refinery reactors,
furnaces: etc., are dependent on the chemical classes and isomer structures of the' feed
stock components. For example, straight chain (unbranched) hydrocarbons are easier to
crack than highly branched structures. Paraffins are more easily cracked than ring
structures such as naphthenes and aromatics, Unsaturated components such as olefins
and aromatic rings can be saturated with hydrogen in hydrocracking and hydrotreating
reactors, etc,

There is another complicating factor for many of the refinery reactors, namely, the
number of reactions taking place. The feed stocks for fluid catalytic cracking units have
hundreds of actual' components of various chemical classes, carbon numbers, and isomer
structures. These pure components are involved in thousands of reactions that include
cracking, hydrogen transfer, condensation, isomerization, and coking (carbon formation).
Thus, simulation of the catalytic cracking re'actions is an impossible task, both from the
standpoint of representing the feed stock with discreet components, and in definition of
the reactions that occur. This is also true of many of the other refinery reactor units, such
as reformers, hydrocrackcrs, cokers, etc.

Prediction of the heat of reaction is also a problem. Ciassic rca~tor calc~!Zitions compute
the standard heat of reaction as the difference in the sum of the heats of formation for the
products and the n~actants. However, it is not possible to predict accurate heat of
formation data for the pseudo-components since they represent a mixture of pure
components of various classes and structUf'es. As Table 5,1 illustrates, the heats of
formation for hydrocarbons vary significantly with the chemical class.
}, '.

!i" 5.4
Simulation of Laboratory Tests
Difficulties in prediction of the laboratory distillations, particularly the initial and end
point temperatures, have been previously discussed in Section 5.1. Several other
laboratory tests present difficulties because of their dependence on the chemical
composition of the stock and the inability of petroleum pseudo-components to accurately
represent true chemical class and structure.

I) Octanes

It is apparent f.-om the illustration in Table 5.1 that this property cannot be predicted
accurately with pseudo-components. Not only is octane highly dependent on the class of
component, it is also highly dependent on the isomer structure of the component. For
example, normal heptane has an F-I octane of 0.0. The other seven-carbon atom
paraffins have the following octanes:

2-methylhexane = 42.4
3-methylhexane = 52

,
-=_. !
Cha.pler5 41

2-4-dimethylpentane = 92.8.

In addition to anomalies because of hydrocarbon class and structure, there are synergistic
octane effects when one class of hydrocarbon is blended with another. . For example,
olefins blended with aromatics exhibit blending octanes that are several numbers higher
than the pure olefin values.

2) Pour Point, Cloud Point

These tests are a measure of the wax content of a petroleum stream. Waxes are primarily
paraffins with long side chains, or long paraffin side chains attached to other hydrocarbon
structures. Pseudo-component TBP cut-point ranges in the temperature range f5r wax are
typically 50 to 100 degrees F (27.8 - 55.6 degrees C). Wax properties are well disguised
within a pseudo-component of this boiling point range .

. 3) Viscosities

Viscosity is a nemesis to correlate for actual petroleum stream data. Many of the open
literature relationships in commercial simulators are based on pure component data. The
viscosities for petroleum streams with large numbers of components are difficult to
correiate. Some of the early anempts such as Watson, Nelson, and Murphy" are still
state of the art. Watson, Nelson, and Murphy correlated whole stream viscosity with API
gravity and the Watson-Murphy characterization factor. Predicting pseudo-component
viscosities and weight averaging them to determine the average stream value has not been
any significant improvement over simple correlations such as Watson, Nelson, and
\1urphy which predict the average stream viscosity.

The controlling factor in viscosity is chemical composition. Paraffins have higher


viscosities than aromatics in the same boiling point range, etc. Moreover, good chemical
walyses for heavier refinery streams are virtually non-existent. The best indicators of the
actual product viscosities are the laboratory viscosities of the corresponding crude oil
fracti'ons for the straight run products. Some of the refining processes for lubricating oils
preferentially extract a particular class of hydrocarbon to give the lubricating oil a
peculiar viscosity! temperature relationship. r

Predicted viscosities from commercial simulators are order of magnitude accuracy for
light oils, such as light diesel fuel, kerosene, naphtha, and gasoline.~ However, predicted
\'iscosities for ~ea\'ier petroleum fractions and whole crude oil are highly inaccurate and
should nOt be used for process design and decision making. Rather, actual viscosity tests
should be run for the stocks in question, and a viscosity blending method used to predict
Ihe blend stream \iscosities. Some commercial simulators provide for input of stream
'iscosity blending indices,
42 Limitations ofpselldo-compollents

4) Flash Point

The flash point is a measure of the volatile components in a petroleum middle distillate.
Therefore, the accuracy of predictions is dependent on the predicted solubility for light
hydrocarbons in the middle distillate hydrocarbons. Numerous attempts have been made
to correlate flash points for petroleum distillates, and all attempts use the predicted
ASTM D86 10 percent distilled temperature as a correlating parameter. Flash point tests
have limited accuracy because of the procedure itself, even assuming pC'rfect sampling
techniques. Therefore, a predicted flash point within plus or minus 10 to 15 degrees F
(5.6 to 8.3 degrees C) to the laboratory tcst value is reasonable.

5) Vapor Pressure and Reid Vapor Pressure

Real components have the largest effect on vapor pressure and Reid vapor pressure
predictions for petroleum streams. Nearly all of the contribution to the vapor pressure for
a petroleum stream is from hydrocarbon components with five carbon atoms or fewer.
This makes it very important that chromatographic data be used to define the light
hydrocarbons in petroleum streams. Note that the ASTM D86 distillation for a stream is
i.'! inodequate to defi.le pseudo-components to represent hydrocarbons witb fewer than five
/" carl,m atoms. As descri,)"d in SI' .(iOIl 3.2, the D86 distillatiO!! test does not condense
hyd~ocarbons with normal boiling points lower than the specified condensing tempera1ure
1I of 32 - 40 degrees F (0 - 4.5 degrees C). Therefore. a characterization based solely on
the D86 distillation does not properly represent the light components that exert the
I: highest vapor pressures.

6) Cetanes

.~t one time, cetane number was determined in a laboratory test engine. However, it
correlates with the API gravity and average boiling po;nt for petroleum streams and is
now calculated with a standard formula. Since the API gravity and average boiling point
may be accurately simulated, the accuracy of the predicted cetane number is good.

7) Sulfur and Metals

Commercial simulator programs cannot predict these properties. However, when the
distillate fractions for an actual stream have been analyzed in the laboratory to determine
these properties, these data may be supplied to the simulator at the mid-volume percents
of the fractional products and used to develop average blending values for the pseudo-
components. Stream average properties may then be calculated with a reasonable degree
of certainty using the pseudo-component blending values, since these properties tend to
distribute il1 petroleum streams as an increasing function of normal boiling point.

References:

. 24 Watson, Nelson, and Murphy. Ind Eng. Che",., 27, p. 1460, (1935).

t
t,
~
G,

.
'. ; \~
"" "
,
.

t" .:

.~ .. ,. ~.
Chapter 6
Thermodynamics for Petroleum Calculations

For most petroleum processes, the thermodynamics are relatively uncomplicated.


Hydrocarbon systems tend to behave ideally, and component relative volatilities are
nearly independent of pressure. Hydrocarbon water solubilities are small, and
hydrocarbon/water systems may be approximated with simplifying assumptions.

The focus of this chapter is practical, working thermodynamics. A standard textbook in


thermodynamics may be consulted for theoretical derivations. It is also important to
remember that the thermodynamics for petroleum calculations are affected by the feed
stock pseudo-component characterizations, and no thermodynamic correlation can
compensate for inaccuracies in the pseudo-component properties.

6.1
Equilibrium K Values
Equilibrium K values, i.e., (yJ :-')'s, are the fundamental building blocks for nearly all
unit operation calculations. The K values for any given system of components are a
function of the temperature, pressure, and composition of the system. Before the age of
computers, K values were predicted based on temperature and pressure only, with various
concepts such as convergence pressure and multiple charts used to account for
composition effects.

The computer age has permitted more sophisticated prediction of K values using
equations of state. Equations of state based on the Redlich-Kwong" equation have
proven to be the most useful for petroleum systems. The most widely used Redlich-
Kwong equations are the modifications of Soave26 and of Peng-Robinson". These
equations are similar and give equivalent results when properly calibrated or "tuned" to
the system in question.

Two methods are used to tune the above equations of state: fitting of binary interaction
parameters (ki,'s), and adjusting the pure component acentric Jactorsl.o accurately predict
the pure component vapor pressures. The k.'s , are determirfed by regression fitting of
binary vapor-liquid equilibrium data to the equation of state. They represent the non-
ideal interactions between pairs of components. For an ideal pair of components such as
methane and ethane, k,j is equal to zero. For a non-ideal pair of components such as C02
and propane, k" is approximately 0.15. A highly non-ideal interaction such as water and
a hydrocarbon may have a k.. greater than 0.5.
"

The literature' abounds with fitted parameters for the Soave and Peng-Robinson
equations of state. It is important to note that these parameters are based on experimental
data having definite temperature and pressure ranges. Vendors of simulation programs
also provide extensive libraries of parameters to represent operating data for various
43
44 Thermodynamicsfor Petroleum Calculations
processes. How~ver, it is prudent 'for the user of a commercial simulator to ascertain that
appropriate tuning parameters are available in the software when calculations are
required for unusual systems, or when highly accurate results are required.

Pseudo-components present some special problems when using the modified Redlich-
Kwong equations of state. For these components, it is not possible to tune the acentric
factors to match pure vapor pressure data. Furthermore. experimental binary vapor-liquid
equilibrium data are not available to regression t;t the 1\'5. Predictive methods based on
known systems must be usp.d to estimate these parameters. These predictive methods are I
a source of differences when comparing results from commercial simulators.

A variety of modifications have been made to the Soave and Peng-Robinson equations to
improve predictions for systems of non-polar hydrocarbons and polar compounds such as
water, alcohols, ketones, etc. The modifications involve use of a different mixing rule for
calculation of the "a" term in the equation of state and use of a different equation form to
predict the component ".alpha" term that is related to the pure component acentric factor.
However, for most petroleum calculations these specialized modifications are not needed.

While there are numerous other methods to predict K-values for petroleum systems, the
older G"lyson-Strced'" method is the most useful and worthy of further mention. This is
an extension of the Chao-Seader" method and is a semi-empirical approach that uses the
Redlich-Kwong equation of state to determine the vapor fugacity and a corresponding
u"
states model to compute the liquid fugacity. Grayson and Streed extended the range of
the Chao-Seader liquid fugacities and added specific curves for hydrogen and methane
that were based on experimental hydrocracking data. The method has approximate limits
of 800 degrees F ( 427 degrees C) and 3000 psia ( 207 bar), but has been extrapolated to
;i
i! higher temperatures with reasonable results.
. i
il" , 6.2
:i
Effect of Non-Hydrocarbons on K values
11

I
1 Non-hydrocarbon light gases are often present in petroleum processes. These gases
i include H" N" CO, CO" SO" H,S, and NH). The non-ideal mixture behavior
I'
1

I, attributable to these gases is predicted accurately by the modified Redlich-Kwong


equations when using k;s relating them to the hydrocarbon components. III the case of
hydrogen, a modified acentric factor is also used to improve predictions of the hydrogen
solubility i.n the hydrocarbon liquids.

-_._- ------"-'--_.
'''C}lapt.er 6 45

6.3
Hydrocarbon-Water Systems

Hydrocarbons are only slightly soluble in water and for most petroleum calculations
rigorous three-phase calculations are not necessary. A simple model may be used as
shown in Figure 6.1 below.

Figure 6.1
Simple Hydrocarbon-Water Model

VAPOR

FEED
He LIQUID

PURE H20

For the above model, the vapor is saturated with water vapor and the hydrocarbon liquid
is saturated with water according to a solubility relationship. The aqueous phase consists
of pure water. Water K-values are computed as:

where: po = water vapor pressure


Xs = water solubility in the hydrocarbon liquid phase
n = system pressure
When more rigorous treatment is required for the water phase, an equation such as the
Kabadi-Danner'" modification of the Soave equation may be used.
46 Thermodynamics for Petroleum Calculations

6.4
Enthalpies
Enthalpies are typically calculated with thermodynamic relationships that relate the actual
mixture enthalpy to the mix"ture enthalpy in the ideal gas state. That is,

H = H* - 6.H

where: H, H* = mixture enthalpy and mil>.iure ideal gas enthalpy


6.H = deviation of the mixture enthalpy from the ideal gas enthalpy

The ideal gas enthalpy for the mixture is computed as the mole average of the component
and pseudo-component ideal gas enthalpies. Pseudo-component ideal gas enthalpies are
I,; predicted as described in Section 4.4. The enthalpy deviation term is calculated as:
i p
!
6H = {[ T (dV/dT) - V]r dp
o

where: T, P = mi,,'!ure temperature ~nd pressure


V = mixture volume
{ = Integral

An equation of state is used to evaluate the V and (dV/dT) terms in the above expression.
Enthalpies calculated in this fashion using the modified Redlich-Kwong expressions have
proven to be more accurate for petroleum mixtures than older, empirical methods.

6.5
Recommended Methods for Petroleum Systems
It is impossible to recommend specifiC methods without identirying specific commercial
simulators. The recommendations given below are based on the author's experience with
the Hyprotech, Ltd. HYSIM and HYSYS programs and the. SimSci, .Jnc. PROVISION'"
r
I program. The first method listed is the author's preferred method.

1) Heavy Hydrocarbon Systems:

This includes crude and vacuum distillation, Fee malO fractionators and coker
fractionators.

HYSIMI HYSYS: Peng-Robinson with Lee-Kesler enthalpies, Grayson-Streed


PROVISION: Grayson-Streed, Soave RK

- --- .. _--
Chapter 6

2) Light Hydrocarbon Systems:

This category includes gas recovery plants, fractionators and splitters.

HYSIMI HYSYS; Peng-Robinso n


PROVISION: Soave RK

3) Hydrogen-Rich Systems:

Included in this category are reformers, hydrocrackers, hydrotreaters., and hydrogen


plants.

HYSIMI HYSYS: Peng-Robinson, Grayson-Streed


PROVISION: Soave RK (with SimSci alpha), Grayson-Streed
4) Sour Water Systems:

HYSIMI HYSYS: Peng-Robinson (Sour option)


PROV/S/OV: Sour Method (modified Soave RK)

5) Ilydrofluric Acid Systems:

HYSIMI HYSYS: Check with vendor


PROVISiON: Hexamer Method

6) Aromatic Extraction Systems:

A liquid phase activity coefficient model is necessary for these systems. Check with the
vendor for applicable system and necessary parameters.

7) Super-fractionators:

These columns include C2 , C3 , C4 , Cl, splitters, etc. HYSIMI HYSYS and PROVISION
have special k parameters for C2 and C3 splitters. Check with vendors for other super-
' ~
fractionators. When separating close boiling isomers, it is probably necessary to
supplement the \endor supplied k.'s.
'l

8) Light Hydrocc.rbuns Dissolved in Water:

These calculations may be needed for environmental considerations.


'endor for applic<lbility and specific recommendations. Check with the

HYSiMI HYSYS: Kabadi-Danner SRI<, Henry Constants


PROVIS!ON: Kabadi-Danner SRK, Henry Constants
48 Thermodynamics/or Petroleum CalculallOnS

6.6
Thermodynamic "Rules of Thumb"
The following guidelines are based on the author's experience with calculations for
hydrocarbon systems in generaL There is no particular significance to the order in which
they are presented .
j'
. ,,
1) It is necessary to use the Peng-Robinson or Soave RK methods to loe"te (lie true
critica! points of light gas mixtures. They may also be used to predict the phase
diagrams. Pseudo-critical calculations are inaccurate because ofmix"ture non-idealities.

2) Large heat capacities may indicate that the mixture critical point is being approached.
Heat capacity becomes very large and the latent heat becomes zero at the critical point.

3) The vapor density approaches the liquid .density as the critical point is approached.
This may be used as a quick check of distillation column conditions. Large vapor
densities indicate that the column is operating too close to the critical pressure. The
maximum pressure for typical deethanizers is about 475 psia (32.8 bars).

4) \\'2ter has 2n important heat C!I~ct willl hydrocarbons. The heat capacity is
approximately twice that of hydrocarbons and the latent heat is five times as large as
hydrocarbons. For Fee main fractionators it is important to have an accumte rate for the
reactor steam.

5) Water has an important partial pressure effect with hydrocarbons in columns with
steam stripping. An accurate steam flow is necessary to match flash zone temperatures.

6) For hydrogen-rich systems such as hydro crackers and reformers, the heat capc;ties of
the feeds and products are nearly identical in the feed/cn1uent exchanger s.

7) The duty versus temperature lines for mixtures containing hydrogen are curved and not
straight. This can result in system pinches requiring at least one more heat exchanger
shell in series versus calculations which are based solely on the exchanger "F," method.

8) A Joule-Thompson expansion across a valve results in a temperature drop for most


mixtures. Mix"tures containing hydrogen may show a temperature increase.

9) Benzene forms azeotropes with nearly every light hydrocarbon. Accurate prediction
of the benzene distribution in a light-ends column may require use of a liquid activity
I,
coefficient model.

10) Hydrogen sulfide causes large non-idealities in hydrocarbon mix"tures by shifting the
critical point of the mixture.

- - - - _.. _<--- .
j
'Clwrpler6 49

11) Carbon dioxide forms an azeotrope with ethane. It may also solidify in cryogeriic
fractionators.

12) Hydrogen has strange phase behavior. It cannot be condensed, but it can be dissolved
in hydrocarbons at high pressures. The Peng-Robinson and Soave RK methods predict
better hydrogen solubilities in hydrocarbon liquids than the Grayson-Streed method.

13) It is not possible to calculate bubble points for systems containing hydrogen.

14) Alcohol-hydrocarbon systems haVe highly non-ideal behavior and must be calculated
using liquid phase activity coefficients.

15) When applicable to the system, equations of states are always more accurate than
empirical and semi-empirical methods. They also are more thermodynamically
consistent than liquid activity coefficient methods.

16) The relative volatilities of hydrocarbons are nearly independent of system pressure.

17) Hydrocarbons are nearly insoluble in water, allowing approximation of tre liquid
water phase as pure water.

18) In general, hydrocarbon systems composed of the same chemical class behave very
ideally. Thus, an aromatic stream from an extraction process behaves very ideally for
distillation purposes.

19) Small non-idealities for close boiling isomers are very important for super-
fractionators. These may be represented with k's in the modified Redlich-Kwong
'J
equations. While the k's are very small they are necessary for accurate calculations. For
'J
example, the k. for propane and propylene is approximately 0.0089.
'J

20) The Grayson-Streed method cannot predict critical point be ha vi or and should never
be used for systems that may approach the critical point.

21) The Braun KIO K value method and Johnson-Grayson enthalpy method have been
superceded long ago by more accurate methods and are not recommended.

22) Commercial simulators often tune thermodynamic data to the default molecular
weight correlation. Therefore, it is usually not advisable to select another molecular
weight correlation unless absolutely necessary.

23) The Peng-Robinson and Soave RK methods are as accurate as the tuning data
supplied by the simulation program vendor. The methods produce equivalent results.
when properly tuned to the system being calculated.

"'".-
.."

so ThennO<JynamlCSJOr rC:=JtUU;UII' "-" .........- -.... ~ ..-

24) Design Generalities:

The modified Redlich-Kwong equations are more conservative for design than the
Grayson-Streed method ..

Lower molecular weight lean oils absorb more light gases than heavier oils.

Absorbers are very poor recovery devices because of the low tray efficiencies.

Equilibrium vapor or liquid can be re-circulated to an equilibrium stage in any


quantity with no change in the separation.

Thermoqynamics are almost never the cause for distillation calculation failures,
assuming an appropriate method is selected.

The higher the column pressure, the more non-ideal the separations.

Liquid viscosity is usually the controlling property for overall tray efficiency.

;',1
Chapter 6 51
References:

25 Redlich, 0., and Kworig, J. N s., Chem. Rev., 44, 233 (l949).
26 Soave, Giorgio, "Equilibrium constants from a modified Redlich-Kwong equation of
state", Chem. Engr. Sci., Vol. 27, p. 1197-1203, (1972).

27 Peng, Ding-Yu, and Robinson, Donald S., "A New Two-Constant Equation of State",
/nd Eng. Chem. Fund., Vol. 15, No. I, p. 59-64, (1976).

28 Grayson, H. G., and Streed, C. W. , "Vapor-Liquid Equilibria for High Temperature


High Pressure Hydrogen-Hydrocarbon Systems", 6th World Petroleum Congress,
FrankfurtlMain, Sect VII, Paper 20, (\963).

29 Chao, K. C. and Seader, J. D., "A General Correlation of Vapor-Liquid Equilibria in


Hydrocarbon Mixtures", A. /. Ch Journal, Vol. 7, No. 4, p. 598-605, (1961).

30 Kabadi, V. N. and Danner, R. P., " A Modified Soave-Redlich-Kwong Equation of


State for Water-Hydrocarbon Phase Equilibria", /nd Eng. Chelll., Vol. 24, No. 3, p. 537-
541, (1985)
Chapter 7
Practical Distillation Principles

The unit operation of most interest for petroleum calculations is distillation. This is an
energy intensive operation and the economic benefits of an improvement can be
substantial. Furthermore, distillation is somewhat unique in that for most columns there
are hundreds of sets of operating conditions Ihat may be used to achieve the same desired
results, that is, product qualities. Thus, improving an operation by lowering the operating
cost (while achieving the same objective) results in a direct increase in the profitability of
the operation.

There are also improvements in energy efficiency that may be attained in the process ..
design phase with simulation. Simulation permits easy exploration of the entire
anticipated range of operations and selection of a design that has flexibility for future
operations. However, most of the discussion in this chapter focuses on simulation of
existing operations, since this is the usual case in petroleum refining operations today.
\Vhik there is some design work being done, most calculations today are conducted for
improvement, debottlenecking, and troubleshooting of existing columns.

7.1
Theoretical Considerations
The theoretical basis for distillation calculations has been established for many decades.
Distillation columns consist of a series of inter-linked vapor-liquid equilibrium stages or
theoretical trays. The liquid and vapor leaving each tray are in vapor-liqllld equilibrium
and the vapor enters the next higher tray, where it establishes a new equilibrium with the
liquid on this tray. The liquid flows to the next lower tray where it establishes a new
equilibrium with the vapor entering this tray and SO on. The lightest cl'mpon~n:s in the
feed mixture exit with the overhead product and the heaviest components exit with the
bottom product. A column typically has a heat source or reboiler at the bottom, and a
heat sink or condenser at the top. Some condensed liquid is returned to the top tray of the
column as reflux.

Solution of distillation calculations is a trial and error procedure. Temperature and flow
profiles are assumed for all trays in the column and vapor-liquid equilibrium and heat
balances are calculated for each tray. All calculation procedures keep the column
pressures constant. The results from the assumed profiles are used for the next series of
calculations and so forth. Calculations are further complicated by the fact that the
equilibrium K values for the components on each tray are affected by the tray
composit:on as well as the temperature and pressure.

All of the "trey to tray" calculations may be inter-linked into a large set of equations
which describe the heat balances for every tray. the vapor-liquid equilibrium relationships
for every tray. the component mass balances for every tray, and the heat and mass
balances for the entire operation. It is also desirable to add equations to the above matrix
52
'jC/Iaptl?r 7 53

to define process conditions or specifications that must be met by the solution. Since the
calculations are based on steady state operation. all of the above conditions must be
satisfied by the solution.

High-speed computers have made possible the rigorous solution of the large matrices
describing distillation columns. A converged solution is defined as a set of independent
variables for the column, e.g., tray temperatures, flows. heat inputs, etc., which produce a
solution for all of the column equations within certain defined tolerances or errors.
Tolerances are prescribed for the component material balances, the tray heat balances, the
tray equilibrium relationships (usually expressed as the tray liquid b"bble point
condition). the performance specifications. and the tray equilibrium K values. Note that
the la:tter tolerance is required since the K values are dependent on composition. Thus, it
is also necessary to converge the K values in addition to all of the column equations.

Several methods have been devised to solve distillation problems and the literature
abounds with descriptions of these procedures .. All of the methods are iterative in nature,
and produce steady state solutions within prescribed tolerances. The most useful method
for solution of petroleum distillation columns is the inside-out method. This method is
further described in the discussion below.

7.1.1
Inside-out Distillation Algorithm
The Newton-Raphson method was the first method used by commercial simulators to
solve distillation problems. A description of this technique has been published by
3l
Goldstein and Stanfield . The inside-out method (I/O) for solution of distillation
problems was devised by Boston"")] in 1970. Richard Russel!" adapted this method to
the rapid solution of all types of distillation columns, including multi-draw columns with
side-strippers and pumparounds such as are used in the petroleum refining industry.

The Russell modification offers significant advantages in calculation speed and lower
storage requirements versus the Newton-Raphson approach which makes it ideally suited
to use on personal computers as reported by Morris, et.a!." The Russell method also has
a great advantage over the older Newton-Raphson algorithms in that the calculations are
nOt highly dependent on an accurate initial estimate of the solution for convergence.
Consequentl\", the Russell method has proven ideal for commercial simulators .

. As implied in the name, the I/O algorithm consists of two iterative loops: an inside
calculation loop and an outside calculation loop. The inside loop calculations use simple
models for the K values and enthalpies and converge the tray heat and material balances,
and the performance specifications. By using stripping factors and side-stream
withdrawal factors as independent variables, the distribution of components within the
column for any trial solution is always in perfect mass balance. This is an important
feature when performing calculations for columns in which trace component flows in the
products are important, such as super-fractionators.
54 Practical Distillation Principles

In the outside loop, the K values and enthalpies are recalculated with the newly predicted
compositions. If the component relative volatilities have changed by more than the
convergence tolerance, the inner 'Ioop calculations are repeated with the new K values
and enthalpy data. A damping factor may also be applied in the outer loop to avoid
oscillation for systems in which the K values are strongly dependent on composition.

The I/O method is net dependent on accurate column flow profile estimates for
co.nvergence; however, it is always good practice to estimate flows 2S accurately as
possible. Convergence of this method can be enhanced significantly when an accurate
, ! estimate of the column temperature profile is supplied. Temperature data are usually
easier to estimate than flow data, particularly for complex refinery columns.

7.1.2
Column Conventions
The conventions used by all commercial simulators are very similar. Figure 7.1 shows
typical representation of column features. It is important to note that all distillation
calculation methods are derived for theoreticallrays, that is, trays in which perfecl vapor-
liquili equilibriu,n is achieved between the exiting liquid and vapor.

Referring to Figure 7.1, the condenser and overhead accumulator drum are considered to
be the first tray. A net liquid product from this tray is returned to the column as reflux.
Liquid water, if present, is decanted as an aqueous phase. Liquid and vapor products are
withdrawn from the reflux drum. For some columns, only a liquid product is withdrawn
from the reflux drum and the condenser is not truly a theoretical tray. In fact, for many
petroleum columns, the liquid product is sub-cooled below its bubble point. The same
convention is followed, however, and the overhead system is still considered as the first
tray. The top tray of the column is considered to be the second tray for a column with a
condenser. This tray always receives the reflux liquid.

The reboiler, if present, is normally considered to be the highest tray number, N+ I. From
Figure 7. I, this convention represents the reboiler as a kettle reboiler. Most commercial
simulators provide ways to represent other types of reboilers such as thermosiphons.
However, for simulation purposes the kettle reboiler assumption is adequate for most
columns.

Columns may have side liquid and vapor draws and side water draws. Side-stripping
columns may also be attached to a column. Side columns of all types are solved
simultaneously with the main column by the [10 method. Pump-around side draws are
us~d to remove heat from the column and pump-downs (not illustrated) may be used for
side heaters. Finally, note that columns may have multiple feeds.

-- .. _------"---'-----_..
------------- -

'I

,:,
rI-
CMpter7 ss

Figure 7.1
Column Conventions
.-.- -------------,'
,, '
--'!+{ : OVHO
r VAPOR

COf'/DENSER
,
':;:=::::',,-
t" :
,.
2nd Tray OVHD
: REFLUX LIQUID
... -------------~-'
----4-----,-. VWATER
' " WATER
_ _Ji-------~VAPOR
FEED - DRAW

SIDE
STRIPPER
FEED STEAM
PRODUCT

PUMPAROUND
COOLER

__--..+-_____-.. LIQUID
DRAW
Tray N

VAPOR

BOTTOMS

LIQUID

Theoretical tray numbering conventions vary from simulator to simulator. The most
common convention is to number trays from the condenser down to the reboiler starting
with tray one for the condenser (when present). HYSYS designates .lhe condenser-reflux
drum tray as the Condenser and the second tray as tray number one. This simulator also
designates the reboiler (when present) as the Reboiler and tray N as the highest tray
number in the column modeL

For columns with no condenser-reflux drum, e.g., a reboiled stripper, the top tray of the
column is designated as tray one by all simulators. For columns with no reboiler, e.g., an
absorber, the bonom tray of the column is designated as tray N by all simulators.
-
56 Practical Distillation Principles

7.1.3
Initial Solution Estimates

Commercial simulators require the user to supply flow estimates for all column products
except one, either one of the top non-aqueous products, or the bottom liquid product. The
reflux quantity mus: also be estimated, either by the user or by using a program default
,, , value. The first and last tray temperatures are also required for most simulators.

It is good practice to always supply the temperature for the physical top of the column,
i.e., second tray for columns with condensers, since there is usually a substantial
temperature grad.ient from the second tray to the first tray in most columns. While not
required, temperature estimates for side draw trays enhance convergence,

Commercial simulators do not vary the tray pressures during the I/O calculations, The
user is required to supply values for the first and last trays in the column model. A linear
pressure profile is assumed for the intermediate trays. Note that for columns with
c0ndensers, a pressure should always be supplied for the second tray, since there is a
substantial pressure gradient between the column top tray and the condenser. The
I: condenser pressure drop may be as high or higher than the total pressure drop across ali
of the other trays. For crude and vacuum columns, it is especially important that the
pressure of the flash zone of the column be accurate and an additional pressure should be
supplied for this purpose.

7.1.4
Non-converged Column Solutions
11
I,
,

A non-converged column solution is onc in which all of the mathematical equations


describing the column were not satisfied. Therefore, the results are not valid and should
/lot be used for engineering design and analysis. The cause for the non-convergence must
be determined and a fully converged solution developed so a trustworthy analysis of the
column operation is possible. The causes for calculation failures when using the I/O
;: algorithm may be grouped in the following categories: _
11
I I) Improper characterization of the feed stock:

This can be avoided by careful analysis of the stream characterizations before column
calculations are attempted, However, the feed checking step is often omitted in the haste
to secure calculated results for a project. Poor feed stock characterization can result in
unexplainable behavior in the column calculations.

2) Impossible Specifications:

A coJuml. may be over-constrained and hence all of the performance specifications


cannot be met. This is the most common type of convergence failure when using the VD

~----------
57

algorithm and it is signaled by failure.ofthe inside loop to converge. Section 7.2.4 gives
reasonable suggestions for CQlumn specifications that are likely to result.in convergence.

3) Poor Initial Estimate:

This is seldom the problem when using the VO method, since it is relatively insensitive to
initial estimates It is still good practice to provide the best initial estimates possible. In
particular, failure to supply an estimate for the physical top tray for columns with
condensers can be a problem, especially if this causes fTe~ water to condense on the
'column trays for the initial trial solution.

4) FreeWater on the Trays:

Most petroleum processing columns are operated such that water is carried overhead as a
vapor, condensed, and decanted at the accumulator drum. However, some columns may
have free water on some of the trays because of process conditions and it may be
necessary to include water draw-off trays for its removal.

Commercial simulators are not consistent in their handling of fTee water on trays other
than the condenser. Some simulators "force" a solution by assigning a large K value to
the water to carry it overhead in the column. This procedure is accompanied by a
warning message that free water would occur at trays other than the condenser.
Calculations with other simulators may simply fail because no forcing technique is used
and therefore a material balance for water in the column cannot be attained. In either
case described above, the column results are invalid and should not be used. The column
process conditions must be revised and/or a water draw-off tray added to the column
model and the model re-calculated to attain a true solution.

5) Thermodynamics:

Assuming an applicable method has been selected for the calculations, this is almost
I,
never the reason for column non-convergence. For columns in which the K values are
highly dependent on the tray compositions, it may be necessary to use a damping factor
to prevent oscillation of the trial solutions. Oscillation caused by thermodynamics IS
evidenced by failure of the outside loop calculations to converge.

Ill-chosen process conditions can also cause problems. The most COmmon problem is
using a column pressure that is too high, resulting in the tr~y mixtures in some parts of
the column being above their critical points. As the critical point is approached for any
mixture, the liquid and vapor compositions become identical, and the component K
values approach unity. Under these conditions fractionation ceases, both in the real
world and in the simulation calculations. It is usually easier to check for this condition
by inspecting the liquid and vapor densities for the trays. If the vapor densities become
large, i.e., exceed an approximate value of 4.0 Ibs/cu ft (64 kgs/cu m), it may be
necessary to lower the column pressure to avoid supercritical conditions.

,I,i

I,
"
' ... -~ ii,
:,1

11'
I
1
1,1
iii
"
58 Practical Distillation Principles

7.2
Simulation of Existing Columns
While this section focuses on existing columns, the same principles may be applied to
column design. Certain steps are always necessary in the setup, solution, and
interpretation of results for column models.

7.2.1
Gathering the Information
While this step may seem obvious, some engineers expect simulators to solve problems
with little or no information: It is helpful to remember that the calculated results from
simulators are no better than the information on which they are based. Good calculated
results depend on good information about the column, including the feed stock and its
conditions. Several categories of information are needed for simulation of a distillation
column:
11
it I) Accurate Representation of the Feed Stock:
i
This cannot be over emphasized, particularly for cOI1'.plex column calculations such as
I crude and vacuum columns. For some columns it is better to combine the products to
,
li
1
characterize the feed. For example, FCe main fractionators have a very hot vapor feed
which is difficult to analyze accurately (ifat all). It is usually better to build the reed for
these columns from the analyses and rates of the products.

2) Column Operating Conditions:


.;
11
;
These include pressures, temperatures, and internal flows such as reflux. It is good to
i have redundant measurements when possible, since it is usually necessary to reconcile
plant data. There are many sources of inaccuracies in measured data, and data must
I
'. always pass a test for reasonableness when building simulation models.

Accurate measurements of the feed and product conditions are necessary if accurate
calculation of the column duties is desired. Note that is usually best for simulation
purposes to calculate the column duties such that performance specifications are met.
Needless to say, it is reassuring to have duties from the operating data as a validity test
for the model.

3) Product Compositions:

Product compositions may be direct determinations such as a component by component


breakdown from a chromatograph, or indirect determinations such as laborate>ry test
results. Some of the laboratory tests that are useful in defining product compositions are
density, laboratory distillation, and vapor pressure.
Chapter 7 59

'4) PFD Information:

It is critical to have a current process flow diagra:n (PFD) for the column operation. This
provides information on feed and product draw locations, the column tray configuration,
condenser, reboiler, other duty arrangements, and so forth. For example, It IS not
uncommon for FCC main fractionators to have a small jumper line which injects quench
directly into the bottom of the column to prevent coking (carbon formation) Without an
accurate PFD, the engineer may not be aware of this flow.

Some information is available on the PFD regarding the column size and internals. It is
usually necessary to supplement this information with tray drawings, downcomer details,
etc., when raling calculations are desired to test the column operating point for possible
flooding conditions. The rating calculations in commercial simulators are useful for
preliminary analysis of existing columns ..

7.2.2
Defining the Separation Zones

The concept of separation zones is useful in column analysis. A separation zone IS


defined as a column section in which a split between two products occurs. Multi-draw
columns such as crude and vacuum distillation columns have multiple separation zones.
Simple columns with only overhead and bottom products have only a single separation
zone. Note that both rectification of heavy components and stripping oflight components
may occur in a separation zone.

It is important to represent the dislribuled components in a separation zone accurately.


Distributed components are those components that exit in both products leaving the
separation zone. These are the components that fractionate or split. The other
components are non-distributed components, with the heavy non-distributed components
exiting in the bottom product and the light non-distributed components exiting in the
overhead product. Non-distributed components have almost no influence on the
separation, and they may be combined or averaged as desired with little effect on the
calculated results for the column. ~

Within the distributed components, the split may be accurately defined by proper
selection of the key components. The fractionation is based on a desired split between the
key componer.ts. The light key is a light distributed component for which a small, but
definite quantity is present in the bottoms product. The heavy key is a heavy distributed
component for which a small, but definite quantity is present in the overhead product.
Note that trace components do not meet these criteria. The key component concept is
most useful for column sections in which the distributed components are defined as real
components.

Some manipulation of plant data is useful in determining key components. Table 7. I


gives some typical plant data as reported for a fractionator. The compositions and rates
--------,

I
,j
60 -Practical Distillation Principles

! have been tabulated for the overhead and bottom products. From these data as reported,
the separation key components are not apparent. Arbitrary seiectio{l of a heavy
component concentration in the overhead and a light component concentration in the
bottoms may result in an incorrect definition of the separation that takes place in the
column. In fact, an incorrectly defined separation may result in multiple solutions for the
column simulation model.

Note that the separation zone contains only four significant distributed components.
Omission of any of these components in the analysis would result in disastrous results
and conclusions. Observe that there are five non-distributed light components in the
overhead product and four non-distributed heavy components in the heavy product. [n
fact, the C7 plus component may represent several actual components. These non-
distributed components have little effect on the calculated separation.

Table 7.1
Distillation Products
Plant Data
Overhead Bottoms
Product Product
Componem LV Percent LV Percent
i-pentane 2.48
n-pentane 11.07
cyclopentane 8.46
2,2 dimethyl butane 1.17
2,3 dimethylbutane 1.34 trace
2 methyl pentane 46.73 0.39
3 methyl pentane 25.58 2.16
n-hexane 3.01 23.98
methylcyclopentane 0.11 10. \3
2,2 methyl pentane 0.25
benzene trace 3.97
cydohexane 9.20
C7 plus 49.93

Total Flow, Bblslday 2442 7558

The data from Table 7.1 have been transformed to a component recovery basis in Table
7.2. In a recovery table, the percent of each component in the feed that is recovered if I
the overhead and bottom product is tabulated. Note that it is relatively easy to see when
the separation is oCClining upon inspection of the recovery table. Two methylpentane i I
clearly the light key component and n-hexane is the heavy key component. These tw
components define a unique separation for the column. This column has split la
components, that is, the light and heavy key components are not adjacent, with 3 meth) I
pentane lying be~ween them. Co_mponents lighter than the light key do not define
I

--~----

I
61

unique operation for the column nor do components heavier than the heavy cOmponent.
The component that appears between the separation keys also fails to define. a unique
operation. Any separation defined by non-key components is not necessarily unique and
there may be a myriad of column operations that can be used to obtain it Thus, it is very
important to find where the separation is occurring when modeling existing column
operations.

Table 7.2
Distillation Column
Recovery Table
Overhead Bottoms
Product Product
Component RecoveG!% Re!;oveG!, %
i-pentane 100.00
n-pentane 100.00
cyclopentane 100.00
2,2 dimethylbutane 100.00
2,3 dimethylbutane 100.00
2 methyl pentane 97.50 2.50
3 methyl pentane 79.29 20.7!
n-hexane 3.90 96.10
methylcyclopentane 0.35 99.65
2,2 methylpentane 100.00
benzene trace 100.00
cycIohexane 100.00
C 7 plus 100.00

The procedure described above is usually adequate for determining separation keys when
modeling existing columns for which the distributed components are clearly identified.
A more rigorous approach to definition of key components has been suggested by Kister"
in which diagrams are constructed using the method of Hengstebeck"- This approach is
useful for revamp modifications at a new operating point. I

Many of the columns in petroleum refineries have separation zones for which the \
components are not clearly identified. For example, consider the separation zone for
light naphtha and heavy naphtha in a splitter column. Some composition data are 'I.
available for the combined naphtha stream; however, it is usually for the lighl . I:
components which do not distribute to both products and are totally recovered in the light 'i'. I
,
naphtha product. The distributed components are represented in the simulation model as I

pseudo-components, and a reasonable definition is necessary for an adequate column


model. Definition of too few distributed pseudo-components results in a model that I.,
predicts step changes when the operating point is changed. This is a poor representation
of the actual operation in which the petroleum components are a continuum and step I'
changes in the products rarely, if ever, occur when the operating point is moved~
i
,:1
i!
il

, ~'.
:r:~ I"

62 Practical Distil/aI/on rr",c;IJ"~~

Figure 7.2 presents the AsTM D86 distillations for light and heavy naphthas from a
splitting operation. The splitter is being operated to produce a 5-95 gap of 20 degrees F.
The separation zone appears to be small on a D86 basis, being equal to approximately 20
degrees F. However, the limitations of the D86 test in determining the true initial point
for the heavy naphtha and the true end paint for the light naphtha hinder the analysis.

Figure 7.2
Naphtha Splitting Column
ASTM D86 Distillations
400

350 i'
V
300 V
H~VY NAP~ !rH'" ~ i"'"'
I
DEGREESF
250

L
.... !"'""- - E~ ~{:.'TI 1-i Z~ t'JE - .-
~
li
I'! -
200

150 , t..- ..-/


V

r --
"i

100
.-
.; 'I""" NAP!-. ITHA
.1 50
I

1I o
o 10 20 30 40 50 60 70 BO 90 100
lVPERCEiH
ii
,-

2l
In Figure 7.3 the Edmister-Okamot0 method has been used to convert the light and
heavy naphtha distillations to a TBP basis. The normal boiling points for the petroleum
! pseudo-components correspond to the TBP distillations. On a TBP oasis, the separation
zone is from 140 to 245 degrees F. or 105 degrees F. It is important that an adequate
I )lumber of pseudo-components be used to model the feed stock in this boiling range.
1 Note that pseudo-components boiling below 140 degrees F or above 245 degrees F have
/1, little effect on thp. separation in the column.
!-
11
j'I
l,i

/'

11

11
li
1

"" -- "---"--~-~"

II
;{CJlaptler 7. 63

Figure 7.3
Naphtha Splitting Column
TliP Distillations
400

350 J
./ V
--- -
300
~ EAV\ NAP ~THA .........
I..-
250
-
V ~ - -
DEGREES F 200
JI"
'.
./
1/ - SE ARA ION ONE
......... V
150
~-- - .;;;;-;;
-p - - ... -
100

50
'/
~ -- ~ IGH' NAP THA

0
V
o 10 20 30 40 50 60 70 80 90 100
LV PERCENT

Simulation programs are convenient for analysis of pseudo-component separation zones.


A preliminary case can be calculated in which the simulator default cut-point ranges are
used for the pseudo-components. As described in Section 4.1.4, typical cut-point ranges
for the naphtha feed stock to this splitting column would be 25 degrees F. Thus, at least
five pseudo-components would be defined for the separation zone between light and
heavy naphtha. This permits a reasonable representation of the fractionation between
these products and for many engineering studies this would be adequate.

When using a si mulator program it is not necessary to perform the exercise of converting
the product distillations to a TBP basis. Rather, the D86 data for the column feed stock
may be supplied to the simulator for translation into pseudo-components and the column
calcuiations p~rformed. The light and heavy naphtha component flows may be printed
side by side and the number of significant pseudo-components that distribute between
these products may then be easily determined.

If a detailed engineering study were being performed for the naphtha splitting column
described above, the simulator default cut-point ranges would be inadequate and more
pseudo-components should be used in the separation zone. In fact, it is also desirable to

,.5"-
...
64 Practical Distillation l'rmctpte,

increase the separation zone range accordingly when the distillation ranges for the light
and! or heavy naphtha products are being changed for the new operation. A guideline is
to have at least six to eight significant pseudo-components in a separation zone.

7.2.3
Translation of Actual trays to Theoretical Trays

~
All rigorous column calculation methods are based on theoretical trays, in which the
vapor and liquid leaving the tray are in perfect vapor-liquid equilibrium. Unfortunately,
real operating columns are filled with actual trays, not theoretical t(ays. Therefore, the
actual trays in a real column must be represented by theoretical trays in the model. The
C
relationship between actual trays and .theoretical trays is not straightforv,'ard, C
complicating the translation process.

The perfomlance of an actual tray compared to the performance of the corresponding



theoretical tray is designated as the tray efficiency. There have been many mathematical
expressions derived to represent tray efficiency; however, the most use!ul concept in

I distillation problems is the overall efficiency. The overall efficiency usually concerns the
entire column and is defined as follows: Cl

I Overall efficiency ~ No. Theoreticnl trays INo. Actual lrays

Overall efficiencies may be defined for entire columns or wnes within columns and
;
Cl.:,{

I
, ,
enable a direct translation of the column actual trays into theoretical trays. Fractional C
trays are not considered with this efficiency model and the efficiencies are expressed on a
percentage basis. For nearly all columns, the overall efficiencies are less than 100
c
percent and the column has fewer theoretical trays than actual trays. It is imponant to C
note that with this definition of cfiiciency,all trays in .he column model are pCI}:ct
vapor-liquid equilibrium stages for the distillation calculations. f
Various tray efficiency models have been developed and published which refer to single
f
trays or locations on a single tray. These models are not overall efficiency models and ~
they all generally take a similar approach when used for rigorous column calculations.
The trays in the column are first calculated as if they were theoretical trays. Then a C
second step is perfonned for each tray in which the compositions for the tray products are
modified through application of a tray efficiency expression. Thus, the vapor alld liquid

leavillg the tray/or which the efficiency has been applied are 110 longer ill equilibrium.

The Murphrce" tray efficiency model is a popular model available in many commercial
simulators and is presented as an illustration. Murphree developed the following tray

efficiency model:

1(." = ( y" - y",,) I (y'. - 1' ,)

I
Cht1pter 7 65

. where: Yn = actual composition of vapor leaving tray n


Yn.' = actual composition ofvapor entering tray n
Yn = vapor equilibrium composition corresponding to
the liquid leaving tray n

Note that after application of the Murphree efficiency, the vapor leaving a tray is no
longer in vapor-liquid equilibrium with the liquid leaving the same tray, i.e., the tray no
longer corresponds to a theoretical tray in the distillation model.

This approach to tcay efficiency is both convenient and appealing, since the user can
supply the actual trays from the column PFD to a simulator program and use tray
efficiencies to reduce the tray performances such that the actual column operation is
replicated. Commercial simulators encourageJhis line of thinking by providing a variety
of tray efficiency models. Unfortunately, many engineers do not understand that the tray
efficiency models provided by commercial simulators are lIot overall efficiency models.

Nothin!! is ever as simple as it seems and using tray efficiency models other than overall
efficiencies can cause serious problems for column models. The non-equilibrium lit:;uid
and vapor leaving the trays cause uncertainties in heat transfer calculations. For example,
if a tray efficiency model is applied to the top tray of the column, the column overhead
vapor is not saturated and may be superheated or subcooled. This has a direct effect on
the condensing requirement. Moreover, tray efficiency models such as Murphree are too
simplistic for petroleum columns, in which there are a large number of components and
widely varying process conditions. Consequently, no "typical" individual tray
efficiencies have been calculated and reported for petroleum columns, and the user must
take a cut and try approach with the efficiencies to match the actual column.

While the above-mentioned considerations are troublesome, they are not the worst
problems related to using tocal tray efficiency models. The worst consequence of using
local tray eificiencies is that the simulation model is rendered useless for prediction
mode. Manipulation of local tray efficiencies in a distillation model is analogous to the
regression fitting of data to an equation form. The rigorous distillation theory that is
capable of predicting results other than the current column operating point is thoroughly
masked and violated by local tray efficiency models. Thus, the column model is useless
for engineering studies in which other operating points are of interest. In fact, one can
argue that the model no longer corresponds to rigorOllS distillation at all, since the
principle of equilibrium vapor and liquid leaving each tray has been violated. Therefore,
it is strongly recommended that tray efficiency models never be used when modeling
petroleum columns.

On the other hand, models based on overall efficiencies always correspond to rigorous
distillation, since the liquid and vapor leaving every tray are in equilibrium. These
models may be used in predictive mode, since distillation theory will always predi(;t an
answer that is directionally correct for a new operating point. There are few open

,,"
rl~ I'

66 Practical Distll/allon rm""y"'"

literature correlations Jor prediction of overall efficiencies, One 'such correlation based
on data for 54 refinery columns was published by Dtickamer and Bradford" and is
presented in Figure 7.4 below. The efficiency is for the key components and the
viscosity is the average of the feed as liquid at the top and bottom temperatures for the
column For absorbers, the rich oil exit temperature is used.

Figure 7.4
Overall Tray Efficiencies: Refinery Columns
Correlation of Drickamer and Bradford"

100

90
..... .....
80

70 i'......

""'" I'-..
Overall 60
Tray
Effi::ie-::,.. % 5(1

40 ! :-..........
.......
I,
I ! ~, i
30

~.
'!.,:
20
.
:' 10

i'
, o
0,05 0.1 0.2 0.3 0,5 1,0
Feedstock Avg Viscosity. cp

The Drickamer and Bradford correlation was subsequently modified by O'Connell'" to

I improve the predictions for columns with high relative volatilitie~ such as absorbers. The
O'Connell correlation is shown in Figure 7.5, For this method, the relative volatility of
I the key components and the feed liquid viscosity are evaluated at column average
I) conditions. O'Connell based his work on commercial and laboratory column data. While
the methods presented in Figures 7.4 and 7.5 may seem overly simplistic, they are
probably the most reasonable open literatme correlations to date for overall tray
efficiency.

Fortunately, typical overall efficiencies have been determined for nearly all types of
petroleum columns by matching models to operating data. Table 7.3 presents some
typical overall efficiencies for various columns used in petroleum refineries. While these
values have been derived from typical operating data, they are usually conservative and

,I
,I
I
1

I
11
67

may be used for preliminary design. The tray vendor will likely perform more specific .
.calculations based on information specific to his trays to finalize the design.

Figure 7.5
Overall Tray Emciencies .
Correlation of O'Connell'o
100

90

80
~
~
10 "-
'-....
60
Overall Tray r----'
Efficiency, % 50

40 ~
r-...... -... -...
30

20

10

o
0.1 0.2 0.3 0.5 1 2 J 5 10

Relative Volatility of Key times feed viscosity

~-----------------------------------------------

When modeling existing columns it is recommended that a typical overall efficiency be


used to translate the actual trays to theoretical trays. The model may be tuned to the plant
operating data by adding or subtracting theoretical trays. The resultant model may be
used for predictive purposes when a new operating point is investigated. While some
tuning of the model may be necessary for the new operating point, the predicted results
will always be directionally correct.

7.2.4
Defining Performance Specifications
For successful simulation models, it is imperative that column performance specifications
be chosen wisel y. Poorly cho.en specifications are the cause for nearly all convergence
failures when solving distillation problems with the VO algorithm. In general,
specifications for the column model should be the same or similar to those used to control
the actual operation. This requires the simulation model builder to become familiar with
the actual column operation.

h?

!1

'I
r

Practical Distillation Principles


68

Table 7.3
Overall Tray Efficiencies"

Typical No. of Typical Typical No. of


Theoreti\<al Trays
Column Service A\<tl.H\1 Tr~y~ Ov~all Effici~ncy
Simple Absorb/Strip 20 - 30 20 - 30
5-7
2 C
1i Steam Side Stripper
Reboil. Side Stripper 7 - 10
3-4
.~

t'1!
'r.. Reboiled Absorber 20 - 40 40 - 50

.d.,, Deethanizer 25 - 35 65 - 70

i.
i:
Depropanizer
Debutanizer
35 -
38 - 45
Alky DeiC 4 (reflux) 75 - 90
40 70 - 80
85 - 90
85 -90
Ii
:1
i Alky DeiC 4 (no reflux) 55 - 70 55 - 65 _<1

L'
Naphtha Splitter 25 - 35 70 - 75 4
C2 Splitter 110-130 95 - 100
"
I'
:t 200 - 250 95 - 100
I~
C} Splitter
C. Splitter 70 - 80 85 - 90
4-5
4
; 4~
III:.i Amine Contactor 20 - 24
9 - 12
Amine Stripper 20 - 24 45 - 55
1I
20 - 30
Crude Distillation: 35 - 50 50 - 60
30 2
Stripping Zone 5-7
30 I -2
Flash Zone- 1st draw 3-7
45 - 50 3-5
I st Draw - 2nd Draw 7 - 10
SO - 55
3-5
2nd Draw - 3rd Draw 7 - 10
60 - 70 6-8
Top Draw to Reflux 10 - 12

Vacuum Column (G.O. Operation):


1
Stripping 2-4
I I -2
iiJ FI. Zone to HGO Draw 2 - 3
2
,
HGO Section 3-5
2
LGO Section 3-5

50 - 60 13-17
FCC Main Fract.: 24 - 35 2
Quench Zone 5-7
2-3
Quench - HGO Draw 3 - 5 3-5
HGO-LCGO 6-S
5-7
LCGO - Top 7 - 10

For every specification imposed on a column model, there must be a corresponding


degree of freedom or parameter that is not specified, This degree of freedom is allowed
to see~ the level required to satisfy the performance specification equation in the solution.

!
ae

G-

~~rpter7 69

'This implies that the degree of freedom must have an effect on the performance
specification. For example, a debutanizer column is operated such that the Reid vapor
pressure of the stabilized product is 6.5 psi: The plant operator adjusts the reboiler heat
input until the desired Reid vapor pressure is met. For this column, the Reid vapor
pressure is the performance specification and tlie reboiler heat input is the degree of
freedom.

For distillation models, the logical choices for degrees of freedom are the column heat
sources, column heat sinks, and the side product draw rates. Thus, a conventional
a
column with two products, a reboiler, and condenser has two possible degrees of
freedom and may therefore have two performance specifications. For the debutanizer
column example given above, an additional specification .nay be added and the
condensing duty calculated as the corresponding degree of freedom. A logical
specification for this column is the isopentane loss in the overhead product.

In reality, the operator of a debutanizer column controls the top temperature of the
column by setting the reflux rate to control the isopentane loss. The condensing duty is
indirectly changed as reflux is returned to the column. For the simulation model, the
condensing duty is directly controlled as a degree of freedom in the calculations. The
simulation approach is equivalent to the plant approach in controlling the isopentane loss.
Therefore the model replicates the plant behavior accurately.

It is important to recognize performance specifications that are equivalent to avoid over-


specifying a column model. For example, the isopentane loss in the debutanizer model
may be specified as the actual isopentane content in the overhead product, the isopentane
recovery in the bottom product, or the dew point temperature of the column overhead
vapor. Only one of these specifications may be used for the model. Furthermore, it is
known that the isopentane loss is controlled by the column reflux. Therefore, the column
reflux rate cannot also be used as performance specification since it is a needed degree of
freedom for the calculations. As stated above, the reflux rate may be determined
indirectly by selecting the condensing duty as a degree of freedom for the column
calculations.

Note that equivalent specifications are also possible for the debutanizer-bottom product.
The Reid vapor pressure is a measure of the n-butane content in the bottom product.
Therefore, the following equivalent specifications could be used to control the bottom
product: Reid vapor pressure, n-butane recovery in the overhead product, n-butane
coment of the bottom product, and bubble point temperature of the bottom product. Only
one of these specifications should be chosen for the model. Furthermore, it is necessary
to have the reboiling duty as a degree of freedom for the calculations to meet the bottom
product specification.

In reality, successful simulation of the debutanizer column depends on selection of


performance specifications that define the separation of the light and heavy key
components, either directly or indirectly. The light and heavy key components are n-
butane and isopentane. Thus, any pair of specifications that define the light key/ heavy

-$ ri. =t-
I
: i
----"'"

70 Practical Distillation J'rmclples

key separation results in a successful simulation model that corresponds to the actual
column operation. This prins:iple is true for any column and this is why it is so important
that the column key components be identified before the simulation model is attempted.

For some petroleum columns, the key components cannot be identified as known
components. For these columns, the concept of equivalent specifications is very
important in selecting the performance specifications. For example, consider a naphtha
splitting column. The iighi components that are identified ill the feed characterization are
usually all recovered in the overhead product; hence, they may not be used as light key
components for the split. In fact, for this column, the plant operator controls the ASTM
D86 end point of the overhead product to limit the heavy components in this product
I! This [s equivalent to a heavy key component specification, since the D86 end point of a
I1 stream is controlled by its heaviest components. As pre~iously discussed in Sectioll 5. J,
the D86 end point cannot be modeled accurately, therefore the D86 95 percent distilled is
:/1 chosen as the specification for the heavy key component for the column model.
iij!
It is also necessary to choose a light key specification to solve the naphtha splitting
column discussed above. Naphtha splitters are often controlled to produce a desired
11
if ASTM D86 5 - 9S percent gap for the products. The gap is defined as the D86 five
pc,rcent distilled of the heavy product minus the DS6 ninety-five percent distilled for the
light product. Note that the gap specification is an icc:irect wa; to define the D86 five
percent distilled temperature of the heavy product. The five percent distilled temperature
of a stream is detennined by the lightest components in the stream. Therefore, a gap
specification for the splitting column is equivalent to a specification of the light key
separation component. Thus, for the naphtha splitter, the light keyl heavy key separation
is defined by the D86 ninety-five percent distilled point for the overhead product and the
" D86 5 -9 5 gap for the bottom product.
i For some columns, both liquid and vapor products are withdrawn from the reflux drum as
illustrated below in Figure 7.6. The liquid! vapor split on the condenser drum provides
another degree of freedom and performance specification for the column model.

Figure 7.6
Mixed Phase Condenser

Condenser

Overtlead /' Vapor Product


Vapor
Reflux
Drum
I I Top Tray
I Reflux Liquid Product

,
i I
I j' !
'1
"
!!'t"

r
Chapter 7 71

Simulation programs define the liquid product from the condenser drum as a side liquid
draw and the vapor product as the overhead product for this arrangement. Thus, the
condenser side liquid draw is available as a degree of freedom for the calculations. Since
the reflux drum is a theoretical tray, the liquid and vapor products leaving the drum must
be in vapor-liquid equilibrium. Under these conditions, there is only one temperature that
satisfies any given liquid! vapor product split from the condenser drum.

It is always good practice to allow the condenser side liquid draw rate to be a degree of
freedom for the calculations, with its rate calculated to meet a performance specification.
For condensers with small vapor product flows, it is best to specify the vapor flow and
allow the condenser drum temperature to be calculated. This produces the most stable
model, particularly .if it is planned to explore alternate operations that may alter the
composition of the overhead vapor to the condenser. For condensers with significant
vapor product flows, the condenser temperature may be used for the performance
specification and the vapor product flow calculated to satisfy the equilibrium balance.
with the liquid product flow.

7.2.5
Tray Ratirlg
Commercial simulation programs provide various correlations for tray rating. These are
typically vendor supplied chart methods, such as the design manuals ofGlitsch", Koch",
and Nutter.... These methods are generalized and not necessarily the same as those used
by the same suppliers when guaranteeing equipment. The above three chart methods are
all for valve trays. No such chart methods exist for older type trays such as bubble caps.

It is doubtful that the generalized tray rating methods in commercial simulators can
adequately rate specially designed trays. In fact, some commercial simulators
approximate the performance for non-valve type trays by applying factors to valve tray
ratings. In other words, ratings from commercial simulators may not be applicable or
accurate for your column. Therefore it is good to know what methods are being used in
the program for rating and design calculations. Kister" discusses,some of the problems
encountered when relying on simulator hydraulic calculations for design.

While the correlations in commercial simulators are not accurate enough for design of
trays, they are still useful for troubleshooting and preliminary sizing work. Apparent
flooding factors, downcomer backups, and tray pressure drops are estimated by most of
the commercial simulators when tray and downcomer details are supplied. These results
are useful for checking purposes to indicate possible operational problems within a
column. More rigorous methods must always be used to finalize tray calculations for
revamps and designs.

Correlations are also provided in commercial simulators for packed columns. However,
the actual column calculations are always based on theoretical trays which means that
72 Practical Distillation PrincIples

HETP (height equivalent to Iheoretical tray') must be assumed for the packed sections in
the initial setup of the simulation modeL HETP's vary for packings, and depend on
packing type and size, column loadings, column diameter, and a variety of other
operating parameters. The accuracy of packing calculations is dependent on the quality
of the packing data and the applicability of the pressure drop methods used in the
commercial simulator. As with tray ratings, it is important to know the limitations and
accuracy of the methods and data being used for the packing calculations.

7.3
Troubleshooting Actual Columns
!j
. I
I, All troubleshooting with computer simulation must be based on mathematically
.'
converged column solutions. It is not possible \0 reach valid conclusions using
simulation models for which the column mathematical constraints are unsatisfied.
Therefore, the first and necessary step when troubleshooting must always be to obtain
converged results with the column modeL It is further necessary to have column models
that can be used in predictive mode for troubleshooting. Thus, models based on local
tray efficiency models are of no value for troubleshooting because they cannot reliably
[)redict an alternate operating p,~,int. This section discusses troubleshooting from two
perspectives: difficulties in repli~ating the real column operation and using models tJ
help troublcshoot operational problems.

7.3.1
Difficulties Matching Real Column Operations
Computer simulation has been successfully applied to petroleum distillation problems
ior many years. Surprisingly, the necessity of representing petroleum mixtures with
pseudo-components has not been a serious hindrance to the development of accurate
models. Therefore, when a computer model does not match the actual operation, there
must be an explainable reason. In this section, it is assumed that the column is operating
normally and there are no operational problems. Section 7.3.2 discusses problems
attributable to column operational problems.
I,
Differences between the model and the plant are commonly reflected in the column
temperatures, product compositions, product rates, product properties, top reflux rates,
internal liquid flow rates, and heat duties. A step-wise approach is always best when
reconciling models to plant data. Several suggestions are listed below,

I) Feed Characterization:

This is the most important step in any modeling project. Great care should be used to
model the column feed stock as accurately as possible, For Ci'ude and vacuum systems,
some special techniques are necessary and these are discussed in Chapters 8 and 9. Some
general guidelines for feed characteriz.ation are as follows:
73

a. Use the best current data available for the feed stock.

b. The feed stock analysis can always be checked by blending the characterized products
to reproduce the feed stock. It is especially helpful to superimpose the TBP distillations
for the feed stock and the feed stock as derived from the product blend. If they do not
agree, it will be impossible to match the column material balance with the model.

c. Use multiple sets of petroleum pseudo-components to represent petroleum streams


with different chemical make-ups such as virgin (uncracked) materials and reaction
products.

d. Use intelligent methods to extrapolate all laboratory distillations to 100 percent


distilled. Never rely on mathematical techniques in commercial simulators to properly
extrapolate a laboratory distillation.

e. Always compare the characterized feed stock to the original data.

f It is imperative that a light-ends analysis of the carbon number fi"c and lighter
hydrocarbons be provided for the characterization when accurate ""por pressure
predictions are needed.

g. Choose pseudo-component cut-point ranges wisely. The simulator default ranges are
not always satisfactory. In particular, it is always necessary to include additional pseudo-
components to accurately represent narrow, "heart-cut" products from distillation
columns.

h. Analyze the component spiits in each separation zone of the column to ascertain that a
sufficient number of pseudo-components have been defined. When the column
temperatures and/or side product rates change in a step-wise manner, this is usually a sure
indication of an insufficient number of components in a separation zone. Actual
petroleum columns change in a gradual, continuous fashion when operating changes are
made.

2) Temperature data:

a. Be wary of poor temperature measurements caused by faulty instruments andlor poor


placement of temperature measuring devices.

b. Incorrect simulated temperatures may result from incorrect column pressures. Be sure
to include top and bottom tray pressures in each column model, as well as a condenser
drum pressure.

c. A pressure that is too high results in a predicted temperature that is too high and vice-
versa. If all simulated temperatures in a column are too high or too low but the column
products are satisfactory there is likely a problem with the column pressure profile.
74 PractiCClI Distillation Principles

d. Always supply pressures for flash zones, especially for crude and vacuum units.

e. Make certain the feed temperature is accurate. A feed temperature that is too low
results in a reboiler duty that is too high.

f Bubble point and dew point' calculations may be used to check the reported
temperatures for column products that are saturated liquids and vapors.

g. Reported temperatures and pressures for columns that generate steam such as amino:
regenerators are easily reconciled by using the steam tables.
;.~
h. Column top tray (second theoretical tray for columns with condensers) temperatures
may be easily checked by reconstructing the top tray vapor from the condenser products. J
The true top tray temperature must be the dew. point temperature of the top tray vapor at I
the top tray pressure. This simple model may be used to test the effect of steam, light
gases, and the top tray pressure on the top tray temperature.
J,
I
i. It is not uncommon for simula:ed top tray temperatures for crude distillation columns,
FCC main rrGction"'ors, and coker main fractionatOrs to be higher than the measured I
;)lant values. Th~ best indi(;alion of top temperature agreement with tbe plant data is the
simulated distillation of the liquid overhead product. If the 95 - 100 percent distilled I
temperatures of this product are in reasonable agreement with the plant data, the
:1
simulated top tray temperature should equal the plant value. If it does not, there is
another problem with the plant data which may be inaccurate top tray pressure
measurement, incorrect steam flow in column, differences in light cracked gas rates, or
the effect of liquid entrainment on the temperature measurement.

J. Simulated liquid side draw temperatures are true bubble points. As such, they are
influenced by the light components in the separation zones. An increase in the stripping
of the product below a side product lowers its draw temperature. The number of pseudo-
components used to represent the feed stock also affects the side draw temperatures.
When the relationship of side draw rate to side draw temperature is step-wise instead of
continuous, there are not enough pseudo-components in the separation zone.

k. Column bottom steam has an important effect on the flash zone temperature for crude
and vacuum columns. Unfortunately, steam rates are seldom metered accurately.

I. Some columns such as FCC main fractionators and vacuum columns have bottom
circulation systems which subcool the liquid bottom product. The simulated bottom
product temperature is normally the bubble point temperature and will be higher than the
subcooled temperature. For agreement between the model and the plant, the bottoms
subcooling circuit must be incorporated into the model.

For columns with thermosiphon reboilers, the bottom product temperature is lower than
the reboiler outlet temperature. The normal convention for commercial simulators is to
represent the reboiler as a heat source on the bottom tray of the column. This

" ,.,.
75

configuration corresponds to a kettle reboiler, and the simulated bottom product


temperature corresponds to the reboiler out~et temperature. This simplification in the
column model has no significant effect on the column results, and it is not necessary to
model the reboiler as a thermosiphon reboiler unless design or revamp work is being
done. The calculated reboiler duty is determined by the light key performance
specification and is not dependent on the reboiler configuration used in the model.

n. Free water should never occur in complex columns such as crude columns and Fee
main fractionators. A safety factor of at leas! 2S degrees F (13.9 degrees Cl should
always be maintained in any proposed new operation .. The water dew point temperature
can be easily computed by calculating the water partial pressure in the column overhead
and reading the corresponding temperature from the steam tables.

2) Heat Duties:

a. It is difficult to calculate most reboiler and condenser duties accurately from typical
plant data. Therefore it is best to let the duties be calculated to meet column performance
specifications.

b. Feed preheat temperature has an important effect on the reboiler duty. It is easy to
cross check the duty for feed-bottoms exchangers since the bottom stream is liquid and
the temperatures can be accurately measured.

c. The duty for a pumparound circuit is difficult to calculate using the pumparound rate,
since the rate is rarely, if ever, metered accurately. The pumparound cooler duty should
always be cross checked by calculating the duty for the other side of the exchanger. For
crude column pumparounds, it may be necessary to model additional exchangers in the
train to reconcile the pumparound duties.

d Incorrect steam rates can have a significant heat effect for columns such as Fee main
fractionators because of the high heat capacity of water versus hydrocarbons.

e It is best to specity pumparound duties for crude column and Fee main fractionator
models. The condenser and quench duties for Fee main fractionatorS"" should always be
degrees of freedom for the calculations.

f. The heat balance for FeC main fractionators becomes a critical bottleneck upon
expansion of the column charge rate. It is usually necessary to increase the intermediate
heat removal at the heavy gas oil draw when increas;ng the column charge to keep the
column in heat balance. Most columns are over-sized and column diameter is usually not
as imponant as the heat balance.

3) Reflux Rates:

a Plant top reflux rates are seldom measured accurately. This is especially true for crude
columns and FCe main fractionators.
-
76 Practical Distillation Principles
t
I b. Heat eptimized columns operating at low reflux rates are more sensitive to changes in
the reflux rate than changes to, the number of theoretical trays used in the medel.

c. Sholtcui metheds are sometimes useful in finding the boundary for top reflux rate.
The Underwood method predicts the minimum reflux at an infinite number of theoretical
trays. The Fenske method predicts the minimum number of trays at infinite reflux. The
column operating point must lie between these extremes. Kister" has published a
techniql,le to detennine theoretical trays and minimum top reflux foe p.lulti-componcnt
distillation.

d. When the column separation is met satisfactorily and the top reflux rale is higher than
the plant, the number of theoretical trays in the column model should be increased and
vice versa. This is the best way to determine the column actual O,verall efficiency when
accurate data are available for the column operating conditions and products.

e. The most accurate product rates are based on tank gauges. Orifices should always be
re-calibrated for test runs.

! 4) Test Run Data.

.
I
,
s
,,
a. All test run data have been adjusted 10 show perfect heJt and material balances. It is
always helpful to talk with the test engineer and revisit the origlllai test data when
, reconciling differences between the test and simulation results .
,[

b. It is sometimes helpful to compare test results to typical operating data for the column. I
Significant differences should be explored in more d e p t h ' ; I
c. Simulation can be a useful tool when adjusting test run data, Chemical engineering
theory is a powerful tool when it is necessary to make adjustments to the test data to JI
reconcile the heat and material balances.

d. The best simulation models are those which represent the most typical operation A
model which is based on the average Qperation for a twO or three week period may be
better than one based on a test run of short duration,

7.3.2
Diagnosis of Column Operational Problems
The necessary pre-requisite for troubleshooting with ;::nu!3Iion is a good model for the
normal column operation, It is much better to devel0~ this model before the operational
problems occur since a crisis situation is seldom a f.xJd time for model development.
Real world problems are not always easy to diagno,e. ~~d it is wise to explore as many
facets as possible to confirm probable causes before l~.jng such drastic action as shutting
down and opening up columns. Many good al1i,:~ have been written on column
an d severa I are I'Isted as fu Ither re fiere c:" matena
trou bl es hootmg . I" ' ...
. ,.......,,'"

._----
c

77
,
j ,

column models to diagnose operating problems is sometimes more art than


. science, since model results are based'on theoretical conditions being satisfied. In this I
respect, the model becomes an indicator of how the column may be expected to perform, 11
not how it is performing. Real world problems such as shoes and hard hats in column I

downcomers are n'ot easy to simulate. However, several techniques for using the
simulation data for troubleshooting are suggested below.

I) Checking for Column Flooding:

Operations personnel a/most a/ways suspect column flooding when problems occur.
Therefore, this is always the first issue to resolve when troubleshooting column
operations. Tray rating calculations are useful in indicating possible poor performance
due to flooding of the trays. Calculated flooding factors greater than 100 percent may
indicate tray flooding problems. As previously discussed, the flooding calculations in
commercial simulators are approximate methods and not the final authority.

The separation predicted by a column model is not degraded by flooding; therefore, the
rating calculations can only be used as an indication of possible flooding for the actual
column. In the author's experience with petroleum column~, tray mechanical problems
are far more likely than flooding problems. When using column rating data, do not
neglect to check the predicted downcomer backups and tray pressure drops High
pressure drops and! or downcomer backups greater than 50 percent may also indicate
possible flooding in the actual operation.

2) The Column Temperature Profile:

The column temperature profile is a direct indication of the separation occurring. Zones
of relatively constant temperature in the column indicate tray damage or missing trays. It
is not an uncommon occurrence to have tray manways left open during construction or
turnarounds. Backflow through the column during startup is an effective way to move all
of the trays to the bottom ofa column, resulting in a greatly reduced separation zone.

Chimney tray damage always results in a greatly lowered draw temperature and difficulty
in maintaining a desired draw rate. The product below the draw tray is also lighter than
normal. This is because liquid is leaking from the draw tray to the next section below
and acting as reflux. The leak may be a hole in the draw tray or a bad seal between the
draw tray and the column wall. The latter can be caused by a thermal upset in the
column.

3) Low Tra\' Efficiencies:

The tray efliciencies presented in Table 7.3 are typical for normal column operations. If
it is necessary to lower these values significantly to match a column operation. there may
be tray damage or missing trays. Again, open manways are the same as missing trays. 1

I'

:;,.
78 Practical Distillation Principles

Don't neglect to check for reboiler problems when tray efficiencies seem to be low for an
actual column operation. Remember that separations are accomplished with a
combination of trays and reflux. A problem reboiler may not be generating the reflux
needed for the separation. This is not always apparent since plant reflux measurements
are often inaccurate.

4) Heat Bdancc Problem;;

These occur for complex columns with side draw products and are usually diagnosed by
plant personnel as flooding problems. For these columns, the necessary heat removal to
produce a given set of products is always the same, .regardless of how the duty is
distributed over the column. Thus when side coolers arc not operating properly,
condensing duty is shifted to the overhead condenser. This results in a big increase in the
top reflux for the column, overloading the top section of the column. Correcting the side
cooler operation will correct the apparent flooding problem.

5) Abnormally High Reflux Requirements:

Too much feed preheat is a likely cause for this condition. The column model can be
used to reproduce the plant operation and determine the optimum feed temperature.
When the feed is too hOt there is too much carry up of heavy materials into the
rectification zone. These materials must be washed down to the bottom of the column by
increased reflux. Reflux is generated by increasing the reboiler duty and so on .

.--~----~--
!
ac:
I'fCIK'lpler 7 79

. References:

31 Goldstein, Robert P. , and Stanfield, Robert B., "Flexible Method for the Solution of
Distillation Design Problems using the Newton-Rhapson Technique", Ind. Eng. Chem.
Process Des. Develop., Vo19, No. I, p. 78-84, (1970).

32 Boston, J. F., "A New Class of Quasi-Newton Solution Methods for Multicomponent,
Multistage Separation Processes", Ph. D. Thesis, Tulane University, (1970).

33 Boston, J. F. and Sullivan, S. L. Jr., " A New Class of Solution Methods far
Multicomponent, Multistage Separation Processes", Can. J. Chem. Ellg., p. 52, (Febr..
(974).

34 Russell, Richard A., "A Flexible and Reliable Method Solves Single-Tower and
Crude-Distillation-Column Problems", Chenl.Engr., p. 53-59, (Oct. 17, 1983).

35 Morris, C G. Sim. W. D., Vysniauskas, T., and Svrcek, W. Y., "Crude Tower
Simulation on a Personal Computer", Chem. ElIgr. Progr., p. 63-68, (Nov. 1988).

36 Kister, Henry Z., "TroubIeshoot Distillation Simulations", Chem. Engr. Prog"., p. 63-
75, (June (995).

37 Hengstebeck, R. J., "An Improved Shortcut for Calculating Difficult Multicomponent


Distillations", Chem. Eng., p.IIS, (Jan. 13, 1969).

38 Murphree, E. \.Ind. Eng. Chem., Vo!. 17. p. 747, (1925).

39 Drickamer and Bradford, TraIlS. Am. 11151. Chem. Engrs., Vo!. 39, p. 319, (1943).

40 O'Connell. H. E .. TrallS. Am. Ins1. Chem. Engrs., Vo!. 42, p. 741, (1946).

41 G. L. Kaes, Private Communication.

42 Glitsch, Ballast Tray Design Manual, Bulletin 4900, 5th Edition, (Dec. 1989).

43 Koch, Flexitra\' Design Manual. Bulletin 960-1, (1982).

44 Nutter, Float \'alve Design Manual, Revision 2, (August (981).

45 Kister. Henry Z., "Complex Multicomponent Distillation", Chem. Eng.r., p. 71-80,


(May 13. 1985).

46 Hasbrouck, J. F., Kunesh, J. G., and Smith, V. C, "Successfully Troubleshoot


Distillation Towers". Chem. Elli.". Progr .. P. 63-72. (March 1993).
IP.!'ITT"""

,t:
.. ',
,
80
Practical Distillation Principles

47 Kister, H. Z., and Hower, T. C., "Solve Process Column Problems- Part 1",
r Hydrocarbon Pr., p. 89-91, (May 1991).
I
48 Kister, H. Z., and Hower, T. C., Solve process Column Problems- Part 2",
Hydrocarbon Pr., p. 83-87, (June 1991).
49 Fair, J. R .. and Seibert, F. S., "Understand Distillation-Column Debottlenecking
Options", Chem. Engr. Progr., p. 42-48, (June \996).
SO Kister, H. Z., and Haas, C. E., "Predict Entrainment Flooding on Sieve and Valve
Trays", Chem. Engr. Progr., p. 63-69, (Sept. 1990).

i
\!""I
i'!'
J
Chapter 8.0
Crude Distillation
Crude distillation is the first step in the refining process. The crude oil is heated and
distilled at low pressure into several products with overlapping boiling point ranges.
Most of these products are further refined in downstream processing units. The product
separations in a crude distillation column approximate the product separations in a TBP
laboratory still with one exception. The laboratory TBP distillation is conducted at a
higher reflux ratio than the plant operation and the separations between the adjacent
products are sharper, i. e., there are fewer distributed components in the separation zones.
However, this does not negate the value of the laboratory TBP distillation in predicting
the product yields and product properties which may be expected in a crude distillation
column for a given crude oil.

Crude oil qual ities vary widely around the .globe. Nevertheless, crude oil distillation
units throughout the world operate in similar fashion and achieve similar results,
especially in the separations between adjacent side products. In fact, many crude
distillation units have been designed with the flexibility to process a wide variety of crude
oil types. For example, refineries in the Netherlands purchase crude oil from tankers on
an available basis and may process entirely different types of crude oil on a short term
basis.

Simulation of crude distillation units is important for many reasons. Since this is the first
step in the refining process, any proposed expansion of a refinery begins with a serious
evaluation of the current crude distillation capacity and the steps necessary to expand it.
This i"s accomplished by developing models for the current and proposed expanded
operations and using the models to identify and resolve equipment bottlenecks for the
proposed operation.

Crude distillation models are also useful for investigating the effect of revised crude oil
slates or product requirements on the current operation. However, the most profitable use
of simulation models is often in the improvement of the current operation. Because crude
oil distillation is the first step in the refining process, the charge rate to this process is the
highest of all the refinery process units. This translates to larger equipment (especially
furnaces) and larger utility costs than for the downstream processing units. Because of
the large scale of this operation, a small improvement in efficiency produces a significant
reduction in the unit operating cost. This improves the profitability of the entire refinery.

Data reconciliation is very important when developing crude distillation models. First,
the crude oil feed stock must be represented as accurately as possible. Subsequently,
there are often many questions to resolve regarding the operating data. It is not unusual
that some of the necessary operating data are not available and must be estimated for the
model. For a successful effort, it is imperative that the model builder has a good
understanding of crude oil distillation and the unit being modeled.

81

'!

.~. ,
82 . Crude Distillation

The first section of this chapter provides general background information on the crude
distillation process. Typical flow sheets and operating procedures are discussed. Some
of the typical schemes used to increase unit capacities are also discussed in this section.
The second section presents a stepwise procedure for modeling existing columns. These
techniques may also be applied to development of design models for new columns.

8.1
Crude Distillation Units: General Information
Crude distillation columns and the associated auxiliaries are large when compared to
most other refinery processing units. This book has devoted a separate chapter to
vacuum distillation. However, it can be argued that vacuum distillation is also part of
li crude distillation since it is a continuation of the crude oil distillation process for the
,\
,
heaviest portion of the crude oil.
I .~.

Crude oil distillation columns come in a variety of sizes, with capacities ranging from
f
5,000 to 10,000 barrels! day (700 to 1400 Metric tpd) to 400,000 barrels! day (56,000
Metric tpd). Process economics today favor large units, and many columns processing
,f

less than about 50,000 b2rrels! day (7000 Metric Ipd) have been taken out of service. The
separations achieved with crude columns are independent of size and the op~ra:'ng
strategies are similar for columns of all sizes.
4

There is no industry-wide nomenclature standard for crude distillation columns or their i


. j
products. This can be confusing for new engineers. For example, crude distillation
columns may be called: crude distillation units (CDU's), crude topping units (CTU's),
topping units, atmospheric units, atmospheric pipe-stills, and so forth. f
j

I'
The light gasoline product is called: light straight run (LSR), light gasoline. light naphtha,
etc. The heavy gasoline product is usually reformed to improve its octane and may be
named: naphtha, heavy naphtha, heavy gasoline, reforming naphtha, jet fuel (military JP-
,i
"',
4), etc., depending on its end use. Light fuel distillate is most commonly called kerosene, ,.
but it may also be known as light distillate, jet fuel (commercial JET 50). virgin distillate,
etc. Middle distillate is referred to as diesel fuel, light gas oil (LGO), etc. The heaviest
.., distillate may be designated as: atmospheric gas oil (AGO), heavy gas oil (HGO), heavy
distillate, gas oil, etc. And. finally, the crude column bottoms product is called: reduced.
crude, topped crude oil, atmospheric residue, residuum, atmospheric bottoms, pipe-still
bottoms. etc. In this book, the products described above will be designated as light
straigill nm, hem:)' naphtha. kerosene. diesel. atmospheric gas oil. and topped cmde.

Crude distillation is accomplished in multi-draw columns for which all of the heat is
supplied in the fecd. The products are successively condensed and withdrawn as side
products as the hot vapor portion of the feed rises and is contacted with colder liquid'
reflux flowing dO\'l1 the column. Reflux is provided at the top of the column by pumping
some of the condensed liquid back to the top tray. Reflux is also provided at interrne(jtalte
locations in the column withp1Jmparolllld cooling circuits. The hot liquid portion of

l
1
8 83

oil feed is stripped with steam to remove dissolved light hydrocarbons before
;'i.!C:aVllflg the bottom of the column.

W. L. Nelson" presents four fundamental principles for the operation of crude columns
and other multi-draw columns that are worthy of re petition :

1.. The yield of a given product is primarily a function of the composition of the
feed mixture, not the degree of separation.
-
2. The number oft rays only slightly alters the boiling range of the products as
defined by ASTM initial boiling points and end points.

3. The initial boiling point of side draw products is always low, and'it must be
corrected by either steam stripping or reprocessing.

4. The end point of a side draw product is primarily controlled by opening or


closing the draw valve to change the yield.

8.1.1
Process Description
A general crude unit is depicted in Figure 8.1. Cold crude oil from storage is pumped
through a series of exchangers where it is preheated by exchange with intermediate
products from the crude and vacuum distillation columns. The oil is heated to 250 to 300
degrees F (120 to 150 degrees C), five to six liquid volume percent water is injected, and
the resultant emulsion is fed to an electrostatic desalter. In the desalter, the salts
(primarily chlorides) selectively migrate to the aqueous phase and are withdrawn as a
brine solution.

After desalting, the crude oil contains from 0.25 to O.S liquid volume percent water from i,
solubi lity and emulsion effects. The pressure of the desalted crude oil is raised in a
booster pump and it continues through a preheat train where its temperature is raised by
exchange with hot intermediate streams from the crude and vacuum col~mns. Upon exit
from the last preheat exchanger the oil is heated to the desired column inlet temperature
in the crude furnace. Furnace outlet temperatures typically range from 630 to 725
degrees F (333 to 385 degrees C), depending on the crude oil composition.

The hot oil mixture from tne furn::ce flows through a tra:1sfer line into the flash zone of
the main crude column. Here it mixes with the steam and light hydrocarbons from the
column stripping zone. Sufficient steam is heated and introduced into the stripping zone
to strip the lightest hydrocarbons from the topped crude product. The stripping steam
also lowers the panial pressure of the hydrocarbons in the column flash zone. The lower
partial pressure for the hydr:lcarbons lowers the temperature required to distill the
overhead products from the column feed.
84 Crude Distillation
The hot liquid. from the flash zone drops through the column stripping section, where it is
stripped by steam injected into the bottom of the column. The hot vapors from the flash
zone rise and are contacted by cold er reflux flowing down the column. The reflux
condenses the side liquid products. Reflux is provided by the overhead condenser and by
pumparound circuits in which side draw liquid is pumped through exchangers and cooled
by exchange with crude oil in the preheat train. The cooled pump around liquid is
typically retumed to the column It few trays above the draw tray. Pumparound flow rates
are high, because heat is being exchanged with crude oil that is at a high flow mte.

Figure 8.1
Typical Crude Distillation Unit

Condenser

\/\let GaS

LPG

Reflux
vJ.;ter
,----- __ J___1 :
,---_ _ LIght
Straight RUn (
, Stabilization:
r-----:::-=o-..f Fnd :
Top
PIA
~h.pJiJlj.nQ,-____
Stripper
!__
-r... ..... H,ea.,'Y
Napht:13

4
! - - - - - + Kerosene
f----=='-,
Crude
Mid C
PIA
Oil Stripper
' - - -... Oiesel
, ~

Oesalter
Stripper
'------Gas Oil
,
Charge Booster Preheat Furnace f
Pump Pump
Steam ' - - - - - - - - - - - T o p p e d Crude C
~
The pumparound cooling circuits accomplish three objectives. First, they remove latent f
:;
heat from the hot flash zone vapors and help condense the side products. Secondly, they
improve the efficiency of the crude preileat train by enabling heat recovery at higher
temperature levels than the overhead condenser. This decreases the required crude
furnace duty. Finally, they reduce the vapor flow rate through the column which reduces
the required size of the column. Since crude column sizes are primarily determined by the
vapor 110w rates, the pump around cooling is impo!1ant when designing and expanding
these columns. linfo!1unately, the pumparound circuits degrade the fractionation
between side products by reducing the internal liquid flows between side products.

--~~--
8S

liquid side draw products are usually stripped in steam strippers or reboiled strippers
,'rc:m<)ve light materials and control their flash points. Thus, the composition of the
m~ll1test portion of a liquid side product is controlled by a side stripper, not the main
In the case of the gas oil side product, stripping is used to remove diesel boiling
"'. ~.- ... range materials from the cracking stocks for fluid catalytic crackers (FeC's).

The end points for the liquid side products are controlled on the main column by their
draw rates. For example, to increase the end point of the kerosene product in Figure 8.1,
it is necessary to decrease the flow of the diesel product and increase the flow of the
kerosene product. This adjustment allows heavier components to travel up the column to
the kerosene draw tray, increasing the end point of the kerosene product. There may also
be a small decrease in the lightest portion of the diesel product because of this
adjustment, but this effect is small wheil compared to the effect of the diesel steam
stripper.

The unit depicted in Figure 8.1 recovers a combined light straight run! heavy naphtha
overhead product. The separation between these products is accomplished with an
auxilliary splitter column. An alternate processing scheme to separate light and heavy
naphtha is shown below in figure 8.2.

Figure 8.2
Alternate Light! Heavy Naphtha Separation Scheme

Condenser

'---WetGas

L -______~~'
____ J ____
,
LPG
Stabilizer :
~----[----. Light
Straight RurY
Stripper
' - - - - -..... Heavy Naphtha

Note that for this scheme, an additional liquid side draw product is located on the main
column above the kerosene side draw. The heavy naphtha product is withdrawn at this
location and stripped with steam. The light straight run gasoline is removed as the
overhead liquid product from the condenser and stabilized.

The separation of light and heavy naphtha with a splitter column as depicted in Figure 8.1
has at least three advantages over the flow sheet shown in Figure 8.2. The use of naphtha
strippers has been wide! y abandoned by refiners for these reasons.
-
86 Crude Distillation

First, recovering the heavy naphtha with the column overhead products provides a better
measure of operating safety by substantially raising the water dew point for the overhead
vapor from the main column. A safety margin of25 to 35 degrees F (\4 to 20 degrees C)
should always be maintained between the main column overhead temperature and the
dew point of water in the overhead vapor to prevent water condensation in the main
column trays.

The other reasons concern the qualities of the light straight run and heavy naphtha
products. The spliner column provides both better stripping and rectification than the
side stripper and top trays in the crude column used in the heavy naphtha side draw
scheme. I::lence, light materials (five carbon number compounds) may be minimized in
the heavy naphtha reformer feed, and good reforming stocks (carbon number six and
higher) may be minimized in the light straight run gasoline. This improves the
profitability of the naphtha reformer operation.

"'early all of the steam introduced into the main column and the side strippers leaves the
top of the main column as steam. It is condensed and withdrawn as an aqueous phase
free: the condenser accumu\;<tor drum. Chemicals are injected into the main column
overhead vapor line 1O minimize corrosion caused by hydrolizatiol1 of sails in the
condensed water. A small amount of water leaves the process dissolved in the toppcj
crude and side stripper liquid products. Refmers sometimes use reboilcd :;ide s!rippers to
control the flash points ofside liquid products while keeping the products dry. Reboiled
side strippers reduce the vapor load for the main column versus steam side strippers since
the stripping vapor returning to the main column does not contain steam.

The separations between side products are not precise, and there are regions of overlap
where the heaviest components in one side product also oce"r as the lightest components
in the next lower side product. Main cmde columns typically have 30 to 50 actual trays,
depending on the number of side products being withdrawn. Seven to ten trays are
commonly used between adjacent side products. Pumparound cooling zones may have
two to four trays for heat transfer purposes; however, these trays do not accomplish any
significant fractionation.

The column section between the flash zone and the heaviest side product is of particular
interest. There must be significant liquid wash (overflash) and contact area (trays) to
wash metals and coke forming materials down the column into the bottoms product. This
protects the quality of the heaviest side product and prevents carbonization or coking of
the trays in the wash zone. The quantIty of overflash should not be larger than necessary
since it represents heat supplied in the furnace in addilioll 10 that needed to distil! the
overhead products The quantity of overflash that is necessary depends on the unit design
wd the characteristics of the crude oil being processed. Current design philosophy is to
use six to eight trays in the wash zone and an overflash rate of 3.0 to 5.0 liquid volume
percent based on fresh crude charge. Older column designs (prior to 1970) were based on
two to four wash trays and overflash design rates of 10.0 to 15.0 volume percent of fresh
crude charge.

~'-------------.-
'J/rOplrer8 87

'8.1.2
Typical Operations and Control
There is wide variation in the operating conditions used for crude distillation. In general,
the distillation takes place at low pressure and the furnace outlet temperature is controlled
to keep thermal decomposition of the crude oil at an acceptable level. Thermal
decomposition of a crude oil is dependent on its chemical makeup. A paraffin base crude
oil cracks more readily than an aromatic or asphalt base crude oil. Therefore, it is
necessary to process a paraffin base crude oil at a lower temperature than an asphalt base
crude oil. The decomposition (cracking) of crude oil produces light gases, tar-like
substances, and elemental carbon (coke). As might be expected, a paraffin base crude
produces more cracking gas than an aromatic or asphalt base crude oil.

The pressure of the crude column is controlled by holding a back-pressure on the reflux
accumulator drum. Asphalt base crude oils produce little cracking gas and it may be
necessary to use an external gas source to maintain a desired positive pressure on the
accumulator drum. Figure 8.3 presents a typical pressure control scheme used for crude
column accumulator drums. A double control valve arrangement is used to bleed
external gas into the accumulator drum as needed to maintain a desired pressure. When
sufficient gas is produced from the crude oil, the external gas flow is zero.

The pressure of the accumulator drum is usually in the range 3.0 to 5.0 psig (1.22 to 1.36
bar absolute), although some refiners operate at pressures as high as 30 psig (3.1 bar).
A higher pressure reduces vapor loading, but increases the flash zone temperature. The
top tray pressure for the main column is 6 to 10 psi (0.4 to 0.7 bar) higher than the
accumulator drum, depending on the drop through the overhead vapor line and coolers.
The flash zone pressure is usually 5 to 8 psi (0.34 to 0.55 bar) higher than the top tray,
with the furnace transfer line pressure about 5 psi (0.34 bar) higher than the flash zone.

Figure 8.3
Typical Pressure Control Scheme
I" Fuel Gas

Column Overhead
Va r
..
"."j

Wet Gas

Reflux to
Column
Overhead
Water
Liquid
__ !!4!G

88 Crude Distillation

Crude oil charge is first preheated by exchange with crude column products and then
desalted to remove chlorides and other corrosive compounds. Desalters may have one or
two stages and operate in a typical temperature range of 250 to 300 degrees F (121.4 to
149.2 degrees C) and a typical pressure range of 125 to 250 psig (9.6 to.18.3 bars
absolute). Five to six percent by volume water is heated and combined with the crude oil
prior to the desalter operation. In the presence of an electrostatic field, the salts migrate
from the crude oil to the aqueous phase which is drawn oir as brine. Crude oi' from a
good desalter operation has a typical residual water coment 0[0.25 to 0.50 liquid vo:umc
percent. This water includes dissolved water and entrained water.

After water removal, the desalted crude is pumped and exchanged with hot streams from
the crude and vacuum units, prior to the crude furnace. Preheat temperatures ma:{ range
nil from 425 to 575 degrees F (219 to 302 degrees C). The furnace transfer temperature is
;'I,i,
:i
controlled by firing the crude furnace and may range from 630 to 725 degrees F (333 to
385 degrees C), depending on the composition of the crude oil being processed.

The column flash zone temperature is typically 5 to 8 degrees F (2.8 to 4.4 degrees C)
lower than the furnace transfer temperature because of the Joule-Thompson expansion
;,':.TOSS the f"mace tr2nsfer line. The amount of steam used to strip the bottom product
varies gre2tly from unit to unit, with 0.15 to 0.35 lbl gallon (18 to 42 kg! M3) of !'q:J:c
product being some..ilat typical. The required flash zone temperature n,ay be lowered by
using more bottom stripping steam, but this adds more vapor to the coiumn and reduces
the hydrocarbon processing capacity. For a 100,000 barrell day (14,000 M tpd) crude
column, increasing the bottom steam flow from 5,0001bl hr (2270 kg! hr) to 10,000 Ibl hr
,
(4540 kg! hr) decreases the flash zone temperature about 8.0 degrees F (4.5 degrees C)
when producing the same distilled products.

Overflash return to the flash zone is controlled with furnace heat. As mentioned
previously, older designs use fewer wash trays between the flash zone and the
atmospheric gas oil draw and require higher overflash rates to maintain gas oil quality.
Overflash rates of 10 to 15 volume percent of crude charge are not unusual for these
units. Newer units use more wash trays and overflash ranges from 3 to 6 volume percent
of crude charge. Some refmers attempt to withdraw and measure the overflash liquid
returning to the flash zone from the bottom wash tray; however, these measurements are
not usually accurate. It is better overflash control to monitor the quality of the
atmospheric gas oil, in particular col or and Conradson carbon. Another scheme is to
maintain a reasonable temperature drop, 25 to 35 degrees F (13.9 to 19.4 degrees C),
across the bottom wash tray. True overflash quantity is probably best predicted from a
simulation model which has been tuned to match the rate and draw temperature of the
atmospheric gas oil and the flash zone temperature.

Side products are withdrawn on rate control to meet desired end points. Since the main
column has no reboiler to generate stripping vapors, external stripper columns are used to
strip light components from the side products to meet flash point specifications. Side
stripping columns are usually steam, with typical_st.eam flows of 0.12 to 0.15 lbl gallon
stripped product (\4.4 to 18.0 kg! M3). Strip-out of light vapor ran-ges from 10 to 20 %

------_ .. -
8 89

, the hydrocarbon charge to the stripper. 1lte stripping may also be accomplished by
" adding heat via a reboiler instead of stripping steam. The reboiled side stripper has an
advantage in stripping efficiency and results in a product that is dry.

The overhead temperature is controlled with top reflux. The overhead temperature must
be kept 25 to 30 degrees,F (13.9 to 16,7 deg C) higher than the dewpoint temperature for
water at the column overhead conditions so no liquid water is condensed in the column
trays. The dewpoint of the water may be easily determined by using the steam tables as
illustrated in Example 8.1.

From this example it may be deduced that a heavy crude oil requires a high~r overhead
temperature than a light crude oil. A heavy crude oil requires more bottom stripping
stream and produces less overhead hydrocarbon product. Therefore, the mole fraction of
the water in the CDlumn overhead vapor increases. This raises the water partial pressure
in the overhead vapor which raises the saturation temperature for the water. It is
. necessary to increase the column overhead temperature versus the light crude to suppress
condensation of water in the top of the column.

Example 8.1
Determination of \Vater Dew point fOI Crude Column Overhead Vapor:

Data: Water mole fraction in overhead vapor: 0,085


Main column overhead pressure = 34.7 psia (2.39 bars)

The water partial pressure = 0,085 34,7 = 2,95 psi (0,20 bars)

From !he S!eam Tables:


Water saturation temperature at 2,95 psi a = 141 degrees F (60.9 deg C)

Therefore, safe o\'erhead operating temperature = 141 + 30 = 171 deg F (77.6 deg C)

The split between light straight run gasoline and heavy naphtha is easily controlled when
a splilter Column is used, A splitter column can easily achieve a 25 to 30 degrees F (139
to 16,7 deg C) DS6 gap between the light straight run and heavy naphtha, while using a
reflux ratio (UD) of 0,5 or lower. A column with 20 to 25 actual trays is adequate for
this service, The goal for this separation is to recover carbon number five paraffins in the
light straight run and C6 plus paraffins and benzene precursors in the heavy naphtha,
This increases the light straight run octane and also enhances the gasoline yield from the
catalytic reforming process,

For crude columns which have a heavy naphtha stripper, the column overhead
temperature is used to control the end point of the light straight run, Steam stripping is
used to control the initial boiling point of the heavy naphtha, Control for this flow
scheme is not as precise as when an external splifter column is used~' In addition, the
90 Crode Distillatioll
stripped heavy naphtha product is wet' with dissolved and entrained water from the
stripper.

8.1.3
Schemes to Increase Crude Processing Capacity
The crude column is a very large piece of steel and represents a major capital i"vestment..
Designs prior to 1970 had large safety fact()rs, and it is not uncommon to see these older
columns successfully processing more than double the design capacity. Expansion is
achieved through a variety of means discussed in this section. However, replacement of
an existing crude column with a larger column is ra,ely done for expansion purposes.

Typical bottlenecks when expanding crude capacity are the main column capacity, crude
furnace limit, and limits for auxiliary equipment such as pumps and heat exchangers.
The most economic expansion scheme varies widely, depending on the original design
and availability of supplementary equipment to use in the expansion.

Several expansion techniques are discussed in the sections below.

8.1.3.1
Main Column Considerations
Crude columns are typically designed for 80 percent loading of trays on 24 inch (610
mm) spacings and vapor velocities of2.5 to 3.5 ft/sec (0.76 to 1.07 mlsec). The column
design limit is normally vapor loading, and the maximum loading point is at the top of
the column.

A crude column vapor profile is illustrated in Figure 8.4. Observe that the vapor flow
increases continuously from the column flash zone to the overhead vapor line. Addition ,.
of pumparound side coolers reduces the vapor load in the column and hence reduces the
required column diameter for a given crude charge rate. Thus, one way to gain capacity is
to maximize heat removal at pump around side coolers (especially the lower side coolers)
versus removing heat at the overhead condenser.

It is possible to gain some capacity by reducing the steam flows in the column.
strippers may be reboiled to remove the steam vapor in the main column returns with no
ill effects CH1 the main column operation. It may also be possible to reduce the bottom
steam and further reduce the vapor loading. However, a reduction in the bottom steam
will raise the required furnace transfer temperature and increase the furnace duty.
Removal of bottom steam also reduces stripping of the topped crude and increases the .;
charge to the vacuum unit. Thus, this option requires that additional capacity is available
in the furnace and the vacuum column.

Another simple soh,tion is to proc~ssll.heavier crude oil that has less light material to
load the top of the column. Unfortunately, to process a heavier crude oil .

~-----.------.
8 91

illditi()n!11 heater capacity that may not be available. Also, a heavier crude oil produces
- - more topped crude charge to the vacuum unit and may also contain more contaminants
like sulfur that cause metallurgical problems.

Figure 8.4
Main Crude Column Vapor Flows

,
:, No Side Coolers
,,
,
...... ~, 1\

'\~I
'-
o With Side
Cl.
(\') Coolers
>

Top Flash Top Bottom


Tray Zone Strip. Tray

Another strategy is to raise the column pressure. This reduces the vapor volumetric flows
because of the inverse effect of pressure on vapor volume. However, as the column
pressure is increased, the flash zone temperature must be correspondingly increased to
distill the same overhead products in the column. This requires more crude furnace duty
and may not be possible. Some further tuning could be accomplished by increasing the
column stripping steam, but this lowers the required -furnace duty at the expense of
i:Jcreasing the vapor flow. Hence, changing the column operating pressure is not usually
an attractive option to increase column capacity.

The most widely used technique to reduce main column vapor loading is to precede the
main crude column with a pre-fractionator or pre-flash column. This is a relatively
Simple solution, in which the crude oil is heated by preheat with the crude and vacuum
unit side products and flashed into a column which at least partially removes the lightest
products, The bottoms from the pre-fractionator .or pre-flash column are heated in the
crude furnace and charged to the main colt:mn where the heavier products are separated.
92 Crude DistillatIOn

Figure 8.5
Crude Unit with Pre-fractionator Column
Condenser

Wet Gas
.I
v
Water 0 _______

:
l C_,
Stabilization I
:
, -_ _.... Ught
LPG

Straight Run
1--------.-..; and :
:___ SQti.t1i[ly...__-_~_ _ Heavy
:j
Naphtlta .i
Condenser

,.
Ii Renu
Crude
Oil
i; 1
v
-4f--of::) Stripper Reflux Water
Light
i Char3 e Kero L----Heavy Kerosene

I
PUrr."

Top
Booster

,I .
Pump Preheat
PIA
Pre.fractionatDr __ ~ o::Y Steam
Stripper
.. Diesel
Column
i
'i
i,!

I
!I. "
Stripper
'----Gas Oil

Main
Furnace "--'''---J Column

steam
' - - - - - - - - T o p p e d Crude

A crude column with a pre-fractionator column is depicted in Figure 8.5. After preheat,
the crude oil is charged to the flash zone of a pre-fractionation column where the light
products are removed. A side stripper is used to remove a portion of the kerosene boiling
range material on the pre-fractionator column. The bottoms are pumped, charged to the
crude heater, and sent to the main crude column where the fractionation is completed.
This process scheme has several advantages: the vapor loading in the main column is
reduced, the furnace duty is reduced by removal of the light products, and the topped
crude flow to the vacuum column is not increased.

There is wide variation in the process flow for pre-fractionator column! crude unit
column combinations. Design of the system is usually dictated by the availabilty of used
equipment and the preheat level which may be attained prior to the pre-fractionator
8 93

The pre-fractionator column is not reboiled and the feed temperature determines
quantity oflight products that may be distilled from the feed. There may not be a side
product, depending on the design and the heat available for the feed. The number of
actual trays used in a pre-fractionator may vary from 10 to 24, depending on the design.

8.1.3.2
Furnace Capacity Considerations
The crede furnace is a large fired heater. The transfer temperature (outlet temperature) is
controlled by adjustment of the firing. Furnaces are high cost items, and complete
furnace replacement is seldom considered for expansion purposes. Therefore, an
expansion in crude processing capability is usually accomplished with process revisions
that use the existing furnace capacity more effectively. There are three primary ways to
increase utilization of existing furnaces: decrease the transfer temperature, increase the
inlet temperature to the furnace, and reduce the flow oflight materials to the furnace. .

Decreasing the furnace transfer temptrature is usually counterproductive to expansion of


crurie processing capability. Changing to a lighter crude oil may decre<).se the furnace
transfer temperature, but add greatly to the main column vapor loading. Increasing the
bottom steam reduces the transfer temperature at the cost of additional vapor (steam) in
the column. Reducing the transfer temperature for the same crude oil significantly
increases the charge to the vacuum unit.

Increasing the run-up temperature from the preheat train is a viable option to reduce the
crude furnace duty. The preheat train for a crude! vacuum processing operation consists
of a somewhat complicated network of exchangers which heat the crude oil by cooling
the products and pumparound streams from the main crude and vacuum columns. The
pumparound streams are at much higher rates than the products and therefore are a much
larger source of preheat than the products. Many crude units also exchange cold crude oil
with main column overhead to recover the latent heat that must be removed to condense
the overhead products.

Pinch point analysis and other good network tools were invented in the early 1980's for
analysis and improvement of crude oil preheat trains. Through use of these tools,
engineers have been able to achieve significant increases in the heat transferred in preheat
trains without major expenditures for new equipment. Exchanger performance is
enhanced by increasing the heat transfer coefficient and by increasing the driving force
for heat transfer, i.e., the temperature difference between the hot and cold streams in the
exchanger.

The heat transfer coefficient is a direct function of the Reynolds Number for the flowing
fluid. Since Reynolds Number is directly related to the fluid velocity, an increase in the
fluid velocity results in a corresponding increase in the heat transfer coefficient.
Velocities may be increased in existing exchangers by increasing the number of tube
passes and! or revising the shell side baffle arrangement.

"-
94 erode Distillation

Temperature differences in exchanger trains may be improved by rearrangement of the


sequence of exchanger services. When multiple exchanges are made for a hot stream
such as atmospheric gas oil, the first service is at the hot end of the train, with the
subsequent services progressively closer to the cold end of the train. For two hot streams
with temperatures close to the same level, it is better to split the crude oil and link the
ser/ices in parallel eXChangers to keep the driving force high for heat tra"nsfer to the crude
oil. It becomes uneconomic to re"over heal from stre.ams bdc'.v about 300 degrees F
(\49.2 degrees C) with crude oil. -I

Reduction "of the furnace charge by removing light components is also a productive way
to increase crude processing capacity. The simplist way to reduce flow of light materials
to the crude furnace is to add a preflash drum before the furnace as depicted in Figure
8.6. The vapor from the preflash drum is charged directly to the main crude column,
bypassing the crude furnace. The liquid from the preflash drum is pumped through the
furnace. While this scheme reduces the charge to the furnace, it does not reduce the
loading in the main crude column. "I

The most effective way to reduce furnace charge is to add a pre-fractionator cc.iumn to
bOI;' remo,,' :md pn'Cess ligh: materials from the crude oil. This has already been
described in Section 8.1.3.1.

Figure 8.6
Crude Column with Prcflash Drum

Condenser
1

-;& VVet Gas

Crude
"I Stripper
~--N3ter
\.-.:.......~'!!2,L __- Diesel
Preheat
Des alter Stripper

~
,;1 Charge
Srin
Gas Oil

,,' J'
Pump
Preflasn ~--------Topped Crude
Drum

i
I
8 95-

Crude Distillation Units: Simulation of Existing Columns


The majority of crude distillation models that are developed are used to improve or
expand existing operations, To produce a good model it is necessary to have a good
understanding' of the principles of crude oil distillation as well as a working knowledge of
the operation being modeled. While simulation techniques are important, interpretation
and reconciliation of the plant data with the model are far more important.

This section presents a step-wi~ approach to modeling crude distillation units. In


general, the steps should be followed in the sequence in which they are presented. The
simulation techniques in this section may also be applied to the design of new units.

8.2.1
Definition of the Crude Oil
This is the 111051 importar,t step in modeling any crude distillation unit. Nothing in a
model can compensate jor poor represelltation oj the crude oil. Therefore, every effort
should be made to insure that the crude oil representation is as accurate as possible.
Typically, more than 90 percent of the crude oil must be represented with petroleum
pseudo-components. The accuracy of these pseudo-components is highly dependent on
the accuracy of the TBP boiling point curve for the crude oil.

There are two a;{proaches to modeling the crude oil: use of laboratory assay data for the
crude oil, and biending of laboratory data for the products from the crude distillation unit
to reproduce the crude oil. When both types of information are available, the TBP
boiling point curve for the crude oil as determined from the products may be
superimposed on the crude oil TBP distillation from the crude assay. Good agreement
between the crude assay data and the blended crude oil data for the products is
confirmation that an accurate model can be developed for the unit.

8.2.1.1
Crude Assay Data
Crude assay reports usually pro\'ide TBP or simulated distillations for the whole crude
oil. Additionally, distillations and numerous other physical properties are detenninec for
the various boiling point fractions of the crude oil that are collected and removed from
the laboratory TBP still. The boiling point fractions are collected based on the boiling
point ranges for typical crude oil products and correspond to light gasoline, heavy
naphtha, kerosene, light distillate, light gas oil, heavy gas oil, and residuum.

The TBP distillation procedure has been discussed in Section 3.1. It is important to
remember that the maximum temperature which can be measured with this test is in the
range 925 to 975 degrees F (496 to 526 degrees C), depending on the comPosItIon of the
96 erode Distillation

crude oil. The actual TBP end point for crude oil is greater than 1400 degrees F (760
degrees C) according to Nelson' and may exg:ed 2000 degrees F (1094 degt:ees C) for
asphalt base crude oil. Thus, a substantial portion of the boiling point curve for a crude
oil is not defined by this laboratory test.

Extrapolation of the TBP distillation curve to a final boiling point temperature is required
for development of the pseudo-components. The extrcpolation techniques used by
commercial simulators mayor may not result in a reasonable extrapolation and it is
recommended that probability distillation pape~ be used to extrapolate the distillation
curve to a pre-defined end point temperature. The precise value used as the end point is
not critical and an end point temperature in the range 1600 to 2000 degrees F (871 to
1094 degrees C) is recommended, depending on the gravity of the crude oil.

The highest measured temperatures are plotted on the probability distillation paper and a
I straight line drawn through the highest boiling points and the pre-defined end point.
Several intermediate distillation temperatures are read from the line to complete
i deflllition of the TBP distillation curve as illustrated in Example 8.2. Note that an end
I
point less than 100 LV % is chosen on the probability distillation paper.

The boiling curve from the TBP distillation procedure may be experimentally extended
through application of the ASTM Dl160 vacuum distillation method to tbe heavie.st
portion of the crude oil. This test is run at 10 mm Hg pressure and can measure
temperatures up to 1050 to 1125 degrees F (565.9 to 607.6 degrees C) when corrected to
a 760 mm Hg basis. The Dl160 distillation is equivalent to the true TBP distillation for
these temperatures and no correction is applied. The extended distill'ation curve must
still be extrapolated to a pre-defined end point as previously described. However, the
D I 160 exte.nsion improves the accuracy of the predicted flash zone separation in the
vacuum unit that processes the topped crude oil.

The D2887 simulated distillation is not accurate for full boiling range crude oil. By
design the test has an upper boiling point limit of 1000 degrees F (538 degrees C) and the
highest boiling point material in the crude oil is not eluted from the chromatographic
column. The highest portion of the D2887 simulated distillation curve tends to be flat
versus the normally expected upward concave shape. ~

The high temperature simulated distillation (HTSD) measures temperatures up to 1382


degrees F (694.8 degrees C) and is more accurate for crude oil than the D2887 method.
However, both methods produce a simulated TBP distillation that has a paraffin bias. For
aromatic crude oils, the simulated distillation temperatures will be low and corrections
should be applied at temperatures above 500 degrees F (260 degrees C). There are no
standard boiling range corrections for aromatic crude oils and adjustments must be made
as needed to match the yields and properties for the distillate and heavier crude products.
Commercial simulators have conversion procedures for simulated distillations as
described in Section 4.1.3. However, these procedures are not accurate and it is best to
1 I~ supply the simulated distillation data as t~ough they are the actual TBP information.
8 97

"'C'.,amlnle 8.2
Extrapolation of TBP Curve for Crude oil
Data:
Crude API: 24.0
TBP Data: LV % Degrees F
55.0 800
60.0 850
65.0 900
70.0 950
72.0 954
Procedure:
Plot the TBP data on probability distillation paper as shown in Figure 8.7. Arbitrarily
assign an end point temperature of 2000 degrees F since this is a heavy crude oil. Draw a
straight line through the last few points of the TBP data and the end point temperature.
Read LV % distilled temperatures at 80, 90, and 95 % distilled to complete the TBP
distillation.

Figure 8.7
Extrapolation of Crude Oil TBP

2000 /

1550
lJ..
VI 1350 /
/
Cl>
Cl>
~
Ol
Cl>
0 1100
950 /'
900
800
"

50 60 70 80 90 95 99.5
LV % Distilled
98 Crude Distillation

A typical. crude oil assay includes curves,for bothlhe boiling point and the gravity versus
I
percent distilled. The gravity curve data should always be supplied as well as the boiling
point data for accurate characterization of the crude oil. When a gravity curve is not
provided, the gravities of the boiling point fractions collected during the distillation may
be used to approximate the gravity versus percent distilled curve. The gravities for the
boiling point fractions are supplied at their mid-percents on the whole crude oil sample as
shown in Example 8.3 below. While this is not as accurate as supplying a complete
gravity CUD'e, it is always more accurate than relying on the gravity curve predicted by a
commercial simulator.

When a gravity curve is supplied, the simulator will normalize the portion of the gravity
curve represented by the pseudo-components such that the stream average gravity is
matched. In the unlikely event that neither a gravity curve nor dIe properties for the
boiling point fractions are provided in the' crude assay data, the gravities and yields for
the products from the actual crude distillation unit may be used to supply a gravity curve.

The third impOl1ant characterization parameter is the molecular weight of the pseudo-
components. Commercial simulalOrs estimate this property from the normal boiling point
and gravity or a pseudo-componr!l. However, it is difficult to estimate this property
accurately with open literature correlations bec"use of Its strong dependence on
component chemical type. A third correlating parameter to relate the normal boiling
point and gravity to a specific type of petroleum stock is needed for accurate
characterization, e.g., uncracked virgin stock, FCC cracked stock, coker product, etc.
Three parameter molecular weight prediction methods are usually based on proprietary
J
I
information not available for commercial simulator p'rograms. When such correlations
.:1 are available to the model builder, it is highly recommended that a molecular weight
:1 curve be developed c:nd supplicd for the characterization.

In the author's experience, the generalized method of Twu" predicts reasonable


molecular weights for most refining processes. This method and others are provided in
the commercial simulators. The 1980 API Extended Method" predicts the highest
molecular weights of all open literature correlations and designs based on this method
will be more optimistic for crude and vacuum columns than the other methods. A good
comparison of the open literature molecular weight correlations has been published by
Schneider".

8.2.1.2
Crude Oil Data from Product Blending
Crude assay data are not always available or accurate. Furthermore, crude oils are not:
always segregated in storage, and the oil being processed by a refinery may be an.
unknown mixture of several different crude oils. For these cases, it is reasonable to .
predict the composite crude oil properties by blending the properties for the actual
&3tiHution produC!5. This technique may also be used to check a known crude assay
against actual plant yields.

,1--; .
']htIJ71er8 99

. Example 8.3
Supplying a Gravity Curve from Crude Assay Boiling Point Fractions

Data: Whole Crude API = 20.6


Cumu!ative MidLV% Average
Fraction LV % on Crude LV% on crude on crude API
Light Ends' Ll8 Ll8
Gasoline 10.65 11.83 6.51 52.7
Distillate 23.67 35.50 23.67 32.95
Light Gas Oil 3.33 38.83 37.17 26.64
HvyGas Oil 33.29 72.12 55.48 . 18.28
Hvy Resid 27.88 100.00 86.06 4.63

The individual light ends percentages are supplied and the simulator retrieves the
gravities from the Pure Component Library.

ProceG.'ure: The average gravities are supplied at the mid-percentages of the fractions on
a whole crude I:asis as illustrated in Figure 8.8. The simulator normalizes the pseudo-
component portion of the gravity curve such that the whole crude gravity is satisfied.

Figure 8.8
Supplying a Gravity Curve from Crude Assay Boiling Point Fractions

120

P
/92.6
100
)-------- r-L---- -------- -------- -------
,
80
I
I
I Note: he curve insid the dashed li esis
rE presented with pseudo<omp nems
i\

40
i\
20
I
I
I
I
I
..........

r--s :---- ~

o
I

;'-1.18
I
I--- i'"-)
o 20 40 60 80 100
LV'/. Distilled
100 Crude Distillation

To build a crude oil from the products, an accurate set of product properties and rates
musrbe collected. Some data are more readily aVailable than others. The goal is always
to maximize the use of available resources. This translates to using product rates and
qualities from units downstream from the crude distillation unit. Consider the block flow
diagram shown below in Figure 8.9.

Figure 8.9
Block Flow: Crude Oil Processing

Wet Gas
C3's, C4's

Ught Straight
Run

c
0 Kerosene
~
..
S
0 Diesel
!Heav\, t<~p htha
":>
'0
NonCondensibles
i3 Atmos. Gas Oil

Crude Oil
L
c Lt Vac, Gas Oi
0
p
~
~
~
l Topped Crude is
E
:>
Hvy. Vac. Gas Oil

:>
0
co
>
I Vacuum Resi d

There are two finished products from the crude distillation unit: kerosene and diesel.
Laboratory distillations and gravities are routinely reported for these streams. The
atmospheric gas oil is also sampled and monitored; however, not all refiners run full
laboratory distillations on this stream since it is not a fmal product. It may be necessary
to request a laboratory distillation for this stream.

The light products from the crude distillation are produced by stabilization and splitting
of the crude distillation overhead liquid. A chromatographic breakdown for the Cl'S and
C4S is generally available, and laboratory distillations and gravities are commonly run
for the light straight run gasoline and the heavy naphtha. The wet gas from the crude unit
is not routinely sampled and may be ignored when building a crude oil from the products.
8 101

light gases in the wet gas are mainly prQducts of cracking of the crude oil and may be
Ilstimated and added to the model later to complete definition of the crude oil charge to
crude distillation unit.

The topped crude has a very wide boiling point range, ranging from heavy kerosene to
the heaviest material in the crude oil. Other than the gravity, few laboratory data are
available for this stream. Occasionally, a partial laboratory distillation is done to check
the stripping of light components in the crude distillation stripping section; however,
these data are not normally available.

The flash zone in the crude distillation unit separates between the atmospheric gas oil and
the topped crude. Therefore it is necessary to have some boiling point data for the topped
crude oil to properly model the flash zone. In particular, at least a partial laboratory
distillation is needed for the topped crude to. define the distributed components in the
atmospheric gas oil/ topped crude separation zone. If data are not available for the
vacuum unit products, it is possible to fabricate a topped crude oil laboratory distillation
by trial and error as illustrated in Example 8.4. When this technique is used to model the
crude oil, the resultant topped crude oil is not sufficiently accurate fer use as the feed
stock to a vacuum distillation model.

When data are available for the vacuum distillation unit, the vacuum unit products may
be used to model the topped crude oil. The vacuum tower overhead stream is primarily
composed of light liquids and gases from cracking and may be ignored. The light
vacuum gas oil stream may be analyzed with typical laboratory methods. The heavy
vacuum gas oil has a normal boiling point range that extends to. about 1100 degrees F
(593.7 degrees C) and either an ASTM Dl160 or D2887-extended simulated distillation
lJ1ust be used to produce a fulllaborato.ry distillatio.n. Alternately, distillation probability
paper can be used to extend the laboratory distillation for the heavy vacuum gas oil to an
end point of 1100 degrees F (593.7 degrees C). For the most accuracy in the vacuum
distillation calculations, it is best to have a full laboratory distillation fo.r the heavy
vacuum gas oil.

Laboratory distillations are not usually available for the vacuum resid~which is a very
heavy, tar-like, mixture. The flash zone in the vacuum unit separates the heavy vacuum
gas oil and the vacuum resid. It is necessary to build a labo.rato.ry distillation for the
vacuum resid that includes the distributed components in this separatio.n zo.ne to produce
an accurate model for the vacuum distillatio.n unit. If it is not desired to model the
vacuum distillation unit, the vacuum resid may be arbitrarily assigned a laboratory
distillatio.n ranging from 700 degrees F (371.4 degrees C) to 1600 - 2000 degrees F
(871.4 - 1093.7 degrees C), depending on the heaviness of the crude oil. A few
intermediate po.ints may be read fro.m probability distillation paper to complete the
laborato.ry distillation fo.r the vacuum resid.

When the synthesized crude oil is also. to be used to. mo.del the vacuum distillation unit, it
is necessary to. build a more accurate laborato.ry distillation for the vacuum resid. This
may be acco.mplished by using a trial and error pro.cedure to. develo.p a boiling point

11
102 Crude Distillation

CUlVe for the portion of the vacuum resid that overlaps the heavy vacuum gas oil.
Components that boil higher than these distributed components have no effect on the
flash zone separation and may be assigned arbitrary boiling points as defined by a line on
probability distillation paper from the highest boiling distributed component to the
defined end point for the vacuum resid. This procedure is illustrated in Example 8.5.

Example 8.4
Fabricate Topped Crude Oil TBP Distillation

Data: Atmospheric Gas Oil TBP data: LV% Degrees F


95 900
100. 945
Topped Crude Oil API Gravity = IS.5

Rules of Thumb for Crude Distillation Columns:


,
~;

a) LW 95 L V% [atmos gas oil] - TBP 5 LV% [topped crude] = \75-200 degrees F (97-
'! III degrees C)

b) Topped crude 50 LV% =900- 1000 degrees F (483- 538 degrees C)

c) Topped crude 50 LV % - 10 LV % = 250 degrees F (139 degrees C)


Procedure: Choose a 50 LV % for the topped crude and plot it on probability distillation
paper. This point should be approximately 50 degrees F (27.8 degrees C) higher than the
gas oil end point temperatuI c. Set a reasonable end point for the crude oil and draw a line
from the 50 LV % temperature to the end point to define the highest boiling portion of
, the topped crude distillation. This is illustrated in Figure 8.10.
1/,
Subtract 250 degrees F from the 50 LV % temperature to define the 10 LV %
temperature. On Figure 8.10, connect the 50 LV % and 10 LV % teI'}Peratures with a
straight line to define the topped crude boiling points between 10 LV % and 50 LV %.

Subtract 200 degrees F from the atmospheric gas oil 95 LV % temperature for the first
trialS LV % temperature for the topped crude. Extend a straight line from the 10 LV %
temperature through the first trial 5 LV % temperature to define the boiling points
between the initial boiling point and the la LV % distilled temperatures.

Build the crude oil by combining the fabricated topped crude with the other crude
products. Verity the fabricated topped crude with the simple flash zone model shown in
Figure S.ll. If the calculated flash zone temperature is too high, lower the initial point
and redraw the line from 10 LV %. If the calculated flash zone temperature is too low,
raise the initial point and redraw the line from 10 LV % as shown on Figure 8.10.
8 103

~:d .. r .. 8.10
. Fabricate Topped Crude Oil TBP Distillation
1800 #'
;
;
;
- ;
;
;
1000 if -

V
u. FLtem er.
~

'"
:"
'"
0'" 750 /
/ 1/
700

500
It
'

r,\
,,,

~
1st trial

F.l. te tnp rature is high

0.2 5.0 10.0 50.0 99.0


LV % Distilled

Figure 8.11
Simple Flash Zone Model for Crude Distillation Unit

Atmos Gas Oil


,,-----------,
,, & Lighter ~

Overflash Flash Zone


Fabricated
Heat Source
Crude Oil , 1. ___

,,,--- ----- .,,


2
, I
I Stripping
Bottom 3 I
I
Zone
Steam ,
I

, ,
I Topped
1.---------- Crude on
Notes: Use gas oil composition for overflash.
Specify topped crude oil rate and calculate
required heat input and flash zone temperature.
104 Crude Distillation

Example 8.5
Fabricate Vacuum Resid Distillation

Data: Non-asphalt vacuum unit operation with steam stripping.


Vacuum Resid = 10.4 degrees API
Heavy Vacuum Gas Oil TBP Data: LV % Degrees F
90 1000
95 1040
100 1075
Rules of Thumb for Vacuum Columns:

a) Heavy Vacuum Gas Oil TBP 100 %: 1050 - 115Qdegrees F (565.9 - 621.4 degrees C)

b) Initial boiling point of Vacuum Resid: 750 - 875 degrees F (399 - 468.7 degrees C)

c) Vacuu m Resid 50 LV % Distilled:


Non-asphalt: 1150 - 1250 degrees F (621.4 - 677 degrees C)
Asphalt: 1250 - 1350 degrees F (677 - 732.6 degrees C)

d) Vacuum Resid 50 LV % - 10 LV % = 200 - 225 degrees f (Ill - 125 degrees C)

e) LV % of vacuum resid that overlaps the heavy vacuum gas oil: 25 to 35.

Procedure: Choose a 50 LV % temperature for the vacuum resid of 1200 degrees F and
plot on probability distillation paper. Set a reasonable end point and draw a line from the
50 LV % to the end point to define the highest boiling portion of the distillation as
illustrated in Figure 8.12.

Assume that 30 LV % ofthe vacuum resid overlaps the HVGO and plot a temperature of
1075 degrees F at 30 LV %. Connect the 30 LV % and 50 LV % temperatures with a line
to define the boiling point curve for this portion of the vacuum resid TBP.~

Assume that the vacuum resid has a 50 LV % - 10 LV % of200 degrees F and plot rooo
degrees F at lO LV % distilled. Extend a line through the 30 LV % and the 10 LV %
temperatures to define the boiling point curve from the initial boiling point to 30 LV %.

Build the vacuum unit charge by combining the fabricated vacuum resid with the other
vacuum unit products. Verify the vacuum resid with the simple flash zone model shown
in Figure S. \3. If the calculated flash zone temperature is too high, lower the initial point
and redraw the line from the initial point through 30 LV %. If the calculated flash zone
temperature is too low, raise the initial point and redraw the line from the initial point to
30 LV % as.shown on Figure 8.\3. III rare cases, it may be necessary to adjust the
over/ap percelltage to obtaill cfoSllre.

-.
105

v...llre 8.12
Fabrication of TB}> Curve for Vacuum Resid

1900 ,
/

1580 ,/
lJ..
-
1500
/'
e'"'" _.
/
!il' /
0 FL T mpe ature too pw /
., / /
:; 1200

/ _doV
Cii
Q;
c.
E 1075 V
'"
f-

..I: ::< .-
1000

;;;::'
950
............ 1st rial

870 ,
,,
" F.Z. Tem eratur too high

0.25 5 10 30 50 90 95 99.5
LV% Distilled

Figure 8.13
Simple Flash Zone Models for Vacuum Units

Wet Vacuum Unit Dry Vacuum Unit


Hvy Vac. Gas Oil Hvy Vac.Gas Oil
,--~ & Lighter , - - . & Lighter
Coil s t e a m ; t
Reevcle Oil
Fabricated -"""=.., Rash Zone
--''--<+-- Heat Source
Recycle Oil
Fabricated --L-..f=='l
Topped Crude Topped Crude Heat Source

Battom / 2
----~~;;J
Stripping Zone

Steam Vacuum Vacuum


Resid ~-~ Resid
Note: Recycle oil is oil leaving wash grid that returns to furnace.
Recycle oil may be represented as TBP of last 70 % of HVGO
Recycle oil API = HVGO APt - 6.0
Specify vacuum resid rate and calculate the
required heat input and flash zone temperature.
Ignore bottoms subcooling circuits.

I
. j", ,
:1,
I
-
~' ,

106 Crude Distillation

8.2.2
Collection of Operating and Laboratory Data
The general rule is to collect all data that are available for the operation. This will aid
cross checking and reconciliation of data. Inevitably, there will be inaccurate data that
need reconciliation. The following operating data should be collected when possible:

- Crude charge rate to the column


- Steam rates to main column and stripper:;
- Wash water circu lation rate to the overhead condensers
- Charge rate for other feeds to the column or overhead system (if applicable)
- Rates for all products leaving the main column
- Rates for all products leaving side stripper columns
- Rates for all products leaving the overhead system
- Rates for all pumparound streams (net and total)
- Rates for all pumparound cooling streams
- Rates for heating mediums to side stripper reboilers (if applicable)
- Pressures'
Accumulator Drum
Main column overhead
Main column Flash Zone
Main column bottom
- Temperatures:
Accumulator drum
Main column overhead
Main column draw trays
Furnace inlet and transfer temperatures
Main column flash zone
Main column bottom
11 Side stripper bottom temperatures
Return streams for all pumparounds
Exit temperatures for all pumparound cooling streams
Inlet and outlet temperatures for side stripper heating mediums

The following laboratory data are recommended:

- Crude assay data or sufficient product data to construct crude oil as described
in Sec tion 8. J. l.l.
- Component breakdown for light liquid and vapor products
- Lab distillation, gravity, and light ends breakdown for light straight run
- Lab distillation and gravity for heavy naphtha, kerosene, and diesel ... ~
- Lab distillation and gravity for atmospheric gas oil
- Gravity for topped crude oil
- Lab distillations and gravities for vacuum unit products when crude is
constructed from products (see Section8.2.l.2).

li ,i
'X:/KJrpter 8 107

, When the preheat train is included'in the model it is also necessary to collect information
, for the desalter operation and the various process and utility stream flows that are used in
the preheat exchangers.

The feed stock and product rates and gravities should be used to check the unit material
balance before the model building is begun. If the material balance is in error by more
than three or four weight percent, the source of the imbalance should be located and
corrected. Normalizing the data is a poor substitute for locating the problem!

The following rates are likeiy to be inaccurate, especially if the meter factors have not
been updated: top reflu::. rate, pumparound rates, heating medium rates. Notethat these
streams are not products and accurate rates are not needed for operations.

Stripping steam rates are sometimes mis.sing or inaccurate. Side strippers may be
estimated as 0.1 to 0.15 Ibs steam! gallon of stripped product (12 to 18 kg! M3). It is
important to have an accurate measurement for the niain column bottom steam since this
determines the required flash zone temperature. If no data are available, the main column
bottom steam rate may be estimated as 0.12 Ibs/gallon (14.4 kg! M3) and the model
depicted in Figure 8.11 used to tune the estimated rate,

For crude towers, the temperature measurement of the overhead vapor leaving the
column tends to be inaccurate. Interestingly, the measured temperature is always lower
than the simulated temperature when there is a difference. One plausible explanation is
that liquid entrainment in the overhead vapor causes a "wet bulb" effect that lowers the
measured temperature, It is not unusual to have a difference of 15 to 25 degrees F (7.8 to
13.9 degrees C) between the measured and simulated overhead temperatures.

It is useful to check the pumparound exchanger information. Most pumparound


exchangers do not have vaporization of the cooling medium and all heat transfer IS
sensible heat. Therefore, the duty may be easily verified as shown in Example 8.6.

The furnace transfer temperature is a reasonable check on the column flash zone
temperature. The column flash zone is usually about 5 to 7 degrees E (2.8 to 3.9 degrees
C) lower than the transfer temperature because of Ioule-Thompson cooling. The bottom
'stream leaving the main column is typically 9 to 12 degrees F (5,0 to 6.7 degrees C)
lower than the flash zone because of bottom steam.

Main column product draw temperatures mayor may not be accurate, depending on the
point of measurement. It is important to remember that the simulation model draw
temperature is the true bubble point of the liquid product at the draw tray pressure. For a
main column draw that is fed to a steam side stripper, the side stripper bottom
temperature provides a cross-check for the main column draw temperature. The stripped
product is cooler than the liquid feed because of the steam stripping. Typical steam
stripper cooling is: kerosene strippers: 20 to 30 degrees F (11 - 16.7 degrees C)
diesel strippers: 25 to 40 degrees F (13.9 - 22.2 degrees C)
gas oil strippers: 25 to 40 degrees F (13.9 - 22.2 degrees C)
108 Crude Distillation

Example 8.. 6
Checking Pumparound Data

Data: Diesel Pumparound versus Crude Oil

Diesei: Rate 40,000 Lols/day, AP1 = 36.O, Draw = 490 Jegrees F.


=
Return to column = 375 degrees F
,. Crude Oil: Rate = 50, 000 bbls/day, API = 29.0, Inlet = 275 degrees F.
i Outlet = 370 degreesF
Approximate Heat Capacities:
Diesel = 0.62 Btullb-deg F (2.59 kjlkg-deg C)
Crude oil = 0.63 BTU/lb-deg F (2.64 kjlkg-deg C)
Gravity Conversions:
Diesel = 36.0 AP( = 295.4 Iblbbl
Crude = 29.0 A.PI = 308.3 lbl bbl

.C 'ucedure: Compute exchanger duty with formula: Q = V.' cl' delta t

Duty from diesel data = (40,000/24)(195.4)(0.62)(490-375) = 35.1 Ml\.ffiTU/ll!:

Duty from crude data = (50,000/24) (308.3)(0.63X370-275) = 38.4 MMBTUI hr

Conclusion: The pumparound data are reasonably accuri\te. For the model, the diesel
rate is specified as 40,000 bbl/day and the delta t as 115 deg F.

8.2.3
Translation of Actual Trays to Theoretical Trays
Simulation models are based on theoretical trays where a theoretical tray is defined as a
liquid! vapor contact device with perfect mixing. Furthermore the liq'Clid and vapor
leaving a theoretical tray are in perfect liquidl vapor phase equilibrium. Actual column
trays do not accomplish the perfect liquidl vapor separations of theoretical trays.
Therefore, for any column there are fewer theoretical trays than actual trays. See Section
-.2.3 for further discussion on the relationship between theoretical trays and actual trays.

The ratio of theoretical trays to actual trays is cal1ed tray efftciency and is less than 100
on a percentage basis. In fact, the tray efficiencies in crude distil1ation columns are
considerably less than J 00 percent and vary in the various zones of the main column as
shown in Table 7.3. It is helpful to remember that tray efficiency is affected by many
variables. Drickamer, et.al" found that tray efficiency has an inverse relationship with
the viscosity of the tray liquid. Therefore, it is reasonable to expect tray efficiencies to be
lower in the lower zones of a crude column where the liquid viscosities are higher. The
8 109

distillation column is interesting in that all of the heat is introduced in the column
There is no reboiler to provide stripping vapor and the zones of the column above
flash zone have rectification only. Product stripping is accomplished in external
stripper columns. Rectification is controlled by reflux. Since reflux decreases rapidly
from top to bottom in a crude distillation main column, it is reasonable to expect that less
rectification occurs in the lower column zones where the liquid flows are low.

The tray efficiency models provided by commercial simulators are not valid for crude
distillation and should never be used. See Section 7.2.3 for further discussion of tray
efficiency models. The translation of actual trays to theoretical trays should always be
done by the model builder, with the resultant theoretical trays supplied to the simulator.

Engineers are often needlessly concerned about the precision of the translation step from
actual trays to theoretical trays. In reality, the accuracy of the feed characterization far
outweighs the importance of the tray efficiencies and the principles of W. L. Nelson" are
re-stated here for emphasis:

1. The yield ofa given product i5.primarily a function of the composition of the
feed mixture, not the degree of separation.

2. The number of trays only slightly alters the boiling range of the products as
defIned by ASTM initial boiling points and end points.

3. The initial boiling point of side draw products is always low and it must be
corrected by either steam stripping or reprocessing.

4. The end point of a side draw product is primarily controlled by opening or


closing the draw valve to change the yield.

Translation of actual trays to theoretical trays for the various zones of a crude distillation
column is discussed below.

8.2.3.1
Main Column Stripping Zone
The main column stripping zone usually contains 5 to 7 actual trays. Tray efficiencies are
low, and two theoretical trays are adequate to represent this zone. Note that the top
stropping tray in the actual column receives the liquid from the column flash zone.

8.2.3.2
Main Column Flash Zone
There are no actual trays in this zone of a crude column. However, for model building
", purposes it is useful to represent this zone with one theoretical tray as shown in Figure _
14.
110 Crude Distillalion

Figure 8.14
Main Column Flash Zone
Bottom Wash
Tray

OVertash
It.-i\- -----
. Crude
Oil J;r --;;.,., Heat Source

vapors

Top Stripping
Tray

Representation of the main column flash zone with a theoretical tray permits the addition
of 2 Cleat so'.'Cce in the column Hash zolle. A specification of the ovcrflash rate may be
used to determine the heat duty added to the tray representing the flash zone. Th;s lends
stability to the column model and enhances convergence of the distillation calculations.

The stability of the flash zone model shown in Figure 8.14 expedites tuning ofthe crude
unit model. Without this tray and heat source, the column cannot be solved for cases
where a higher feed temperature is needed to produce a positive flow of overflash from
the bottom wash tray. When the model has been tuned, the flash zone tray and heater
may be removed and the liquid from the flash zone fed to the top stripping tray and the
vapor from the flash zone fed to the bottom wash tray.

8.2.3.3
'1ain Column Wash Zone
This zone consists of the trays between the flash zone and the atmosphenc gas oil draw
tray (bottom side product), Old designs have 2 to 4 actual trays in this zone and newer
designs use 6 to 8 trays in this zone. It is necessary to have higher overflash rates for the
old designs to protect the quality of the atmospheric gas oil. The trays in this zone have
'I
low efficiencies because of the low liquid reflux rate. Use one theoretical tray for old
designs and two theoretical trays for newer designs.
~ !:

8.2.3.4
Pumparound Zones
Three pumparounct arrangements are illustrated in Figure 8.15. Scheme (1) is most
commonly used for crude distillation units. Tbis scheme circuli!te~.a cooled pumparound
t1

--~-- - -
8 III

up the column. The pumparound stream is drawn from the same trayas a liquid
The limit for heat transfer is reached when the liquid flowing from the tray
the pumparound return tray disappears. Crude units operate with less heat removal
than the limit to insure that this liquid is always a positive flow. The trays in the cooling
. zone are for heat transfer only. The large flow of pumparound liquid in the cooling zone
creates a region of constant liquid composition that eliminates fractionation.

Figure 8.15 . .
Pumparound Arrangements

----.11L...
-----
---_.
-~ .
r-----"
-----
4---'

Scheme 1: Conventional Scheme 2: Maximum Duty Scheme 3:Cold Reflux

Scheme (2) is similar to scheme (I) except that the pumparound cooling zone is placed
underneath the product draw tray. For this scheme, all liquid is removed from the tray
above the pumparound section (the product draw tray) and the pumparound provides
liquid for the tray below the product draw. This produces a liquid "pinch point" at the
product draw tray and maximizes heat removal from the column.

Scheme (3) uses a "pump down" scheme to remove heat from the column. This scheme
cannot recover as much heat as the other schemes since some of the cold reflux is re-
vaporized by the hot vapor entering the return tray. It has an advantage over the other
schemes in that the tray receiving the cold return still accomplishes fractionation.

For all three schemes the pumparound circuit is represented with two trays: a draw tray
and a return tray. For schemes (I) and (3) the draw tray also serves as the product draw.

Figure 8.16
Net Pumparound Model
Actual Configuration Simulation Configuration

==
't:: _,j
~A
tN,-e_t_p_I..,A_,-I~~rOduct
====: E ,,_ ~roduct
.----0,-,-------1

---"UI-_:::?--l
Note: The temperature of the product is set equal
to the temperature of the Net PIA return.
::iT

..
112 - Crude Distillation

Some times both the product and the pumparound return stream circulate through the
pumparound exchanger as shown in Figure 8.16. For this arrangement, the column
pumparound for the model should only include the net liquid that returns to the column
and its associated cooling duty. A true model for the pumparound exchanger may be
constructed by exporting a stream from the column that includes the net pumparound and
the product draw flows.

8.2.3.5
Side Product Draw Zones

Figure 8.17
Side Product Draw Zones
Actual Configuration: Simulation Configuration:

_3;_ r------, 17
,6

~StriPper
1"'L... ,5
-;.J'--r-~--i"_;' Stripper
-1L L-.. Kerosene _'_'_ l---.. Keror.".::ne
1-------, 1-----,

Diesel Oiesel

Crude Gas Oil Crude Gas Oil

Note: Actual trays shown. Note: Theoretical trays shown.

Crude distillation columns typically have 8 to 10 actual trays between side products. One'
tray is used to represent the pumparound cooling trays (when present). For the lower side
products, two theoretical trays are adequate to represent the fractionation trays in a side
product zone. For higher side products, three or four theoretical trays may be used to
represent the fractionation trays. Figure 8.17 illustrates the simulation configuration for a
typical crude distillation column.

8.2.3.6
Top Section of Main Column
The zone from the highest side product draw to the column top tray has reasonable
fractionation. An aI'erall tray efficiency of 65 to 70 % is recommended for this section
I of the main column.
I 1
8 113

7
L>'~'- Stripping Columns
Steam side stripping columns have 6 to 10 actual trays, depending on the design. They
may be adequately represented with two (author's preference) or three theoretical trays.

Reboiled side stripper columns have 6 to 12 actual trays. The reboiler is represented as a
theoretical tray with a heat source (conventional kettle reboiler is easiest). Three or four
thoeretical trays are adequate to represent ihe column trays.

8.2.4
Crude Column Overhead System
A typical crude column overhead system is shown in Figure 8.18. There are usually at
least two condensers in series, with the first exchanging heat with the cold crude oil in the
preheat train and the second condenser acting as a trim cooler. Water is circulated back
10 the condenser inlet to dilute the organic salt compounds in the overhead vapor and
reduce corrosion in the condensers.

Figure 8.18
Crude Column Overhead System
Actual Configuration Simulation Configuration:
Wash \'Vater Wash
Water Condenser Tray
Condenser
--------------------~
,,
r----+ Wet gas ,...:-:.c-_~, _ Wet gas

...''--'->- Reflux:

~~~-~:r'[r Drum:
, ,
L ___ _
,,
_________ -------1 Was:h

Sour
'---,--+ Water
Ovhd Liquid Ovhd Liquid Sour
'-./ Water
'-./ Water

The simulation configuration is also shown in Figure 8.18. All simulator programs
consider only one heat sink for the condenser. Pumps are also ignored since they have no
effect on the distillation calculations. In Figure 8.18 the water wash circuit is modeled as
an open loop for simplicity, and the total water phase removed from the reflux drum is
split into two streams to correspond to the wash water and the net sour water stream. The
wash water is shown as an external feed to the condenser tray. .

... ,It is necessary to build a sub-model outside the column to include all of the condenser
This may be accomplished by exponing the top tray vapor outside the distillation
114 en/de Distillation

model and building the overhead system using pumps, exchangers, separator drums, etc.
When a detailed condenser configuration is built outside the column model, it is
recommended that the reflux drum temperature and pressure, the reflux flow, and the
wash water flow a\l be specified at the values used within the column model.

Another complication arises when mode\ing crude overhead systems. The model shown
in Figure 8.1 S considers the ovcchead system to be one theoretical tray that has an
external feed (wash water), one heat sink, one net liquid stream (the reflux), and three
external products, i.e., wet gas, overhead liquid, and decanted w~ter. For this model to be
valid it is essential that both vapor and non-aqueous liquid products are produced.

When the crude oil composition is based on crude assay data, the predicted light ends
flow will be considerably lower than the actual wet gas now from the reflux drum. In
fact, it is likely that the condenser wet gas product predicted from the crude assay light
ends will be at zero flow, making solution of the column algorithm impossible Note that
this could also occur if the wet gas is ignored when the crude oil is built from the crude
products.

There are two ways to prevent non-solution of the column because of zero wet gas flow:
model the condenser as a saturated liquid condenser with nO vapor, or add some vapor to
tile crude oil feed prior to its entry into the column flash zone. For the latter method, a
cracking gas flow rate and composition must be estimated if no data are available for the
wet gas.

The flow of the cracked gas depends on the crude oil composItion and the furnace
transfer temperature. For paraffin based crude oil at moderate furnace transfer
temperatures, a cracked gas rate of 5.0 SCFI bbl crude oil (1.8 SCt\lI M3) is reasonable.
For asphalt based crude oil a cracked gas production of 2.5 SCFI bbl crude oil (0.9 SeMI
M3) is suggested. A reasonable composition for the cracked gas is as follows: 50 mole %
methane, 40 mole % ethane, and 10 mole % propane. These estimates are accurate
enough for the simulation of existing columns. For design, more accurate information
should be procured for sizing the wet gas compressor.

8.2.5
Solution Techniques: Inside/ Out Column Algorithm
The inside! out (UO) column algorithm is very effective for clude distillation systems.
Iteration variables include the tray temperatures, tray flows and compositi"ns, tray heat
balances, and tray vaporlliquid equilibrium relationships. Side columns and pumparound
circuits are solved simultaneously with the main column by this method. The tray
pressures must be supplied by the model builder, and are not changed during the solution
process. The solution is based on performance specifications that are supplied by the
user and! or by program defaults.

!: ,, ,
iC~pter8

8.2.5.1
Initial Estimates
The solution procedure is iterative in nature and starts from estimated temperature, flow,
and tray composition profiles. The procedure is robust and most calculation failures are
the result of badly chosen performance specifications. However, the solution process
may be expedited by furnishing reasonable estimates.

In particular, convergence is enhanced by good estimates for the main column


temperature profile. This is easy for crude distiliation and the following temperature
estimates should be provided: reflux drum, column overhead, all product draw
temperatures, flash zone, and column bottom.

The I/O method is relatively insensitive to the estimated column flows. However, it is
good practice to provide reasonable flow estimates for the overhead reflux and all
products for which the rates are not specified.

8.2.5.2
Initial Model Phase
Unconverged columns yield little useful information and the goal is always to procure a
converged solution. In the initial model building phase, there are usually several items of
data for which reconciliation is necessary. It is wise to simplify the performance
specifications as much as possible in this phase to guarantee closure of the column
calculations. The flash zone representation described in Sec/ion 8.2.3.2 is also
recommended to allow tuning of the flash zone temperature during the reconciliation
process.

The following set of specifications is recommended:

Each pumparound: circulation rate and delta temperature

All liquid products except one: flow rate

Condenser with vapor product: condenser temperature

Overflash rate (when using representation in Section 8.2.3.2)

For the first solution trial, the pumparound delta temperatures should be specified as zero.
This forces all cooling to be at the overhead condenser and prevents solution failure
because of incorrect pumparound rate data. The resultant condenser duty is the total heat
removal for the column. When the pumparound coolers are activated by supplying the
actual delta temperatures, the heat removal is distributed down the column. However, the
total heat removal for the side coolers plus the overhead condenser will be the same as
the case with all heat removed at the overhead condenser. . -

,
"
... _---_. __ .. - .

-
116 Crude Distillation

The case with all heat removed at the overhead condenser is useful. Dependil)g o.n the
design, the duty for the side coolers should be 40 to 70 percent of the total condensing
duty. Furthermore, the case with all cooling at the condenser represents the best product
separation possible since the reflux throughout all column zones is maximized. The
product separations for this case should be better than those attained in the actual plant
(for accurate product rates). Therefore, this case may be used to verify the theoretical
trays used in the various separation zones in the column.

The trim heater duty at the flash zone tray should be small and the flash zone temperature
should match the plant data within a few degrees Fahrenheit. If this is not the case, there
may be a problem with the topped crude oil flow rate, overflash quantity, bottom steam
rate. and/ or the crude oil composition.

8.2.5.3
Tuning the Model
The premise for this section is that the major data problems have been resolved in the
initial i",odel buik'ing phase The model can now be made general and tuned.

Ti-.= furnace transfer temperature should be adjusted such that the flash zone heater has nl'
du:),. This heater is no longer needed and may be removed from the model. Optionally,
.,
:j
the flash zone tray may also be removed, with the flash zone liquid fed to lhe top
st:-ipping tray, and the flash zone vapor fed to the bottom wash tray.

T:'e performance specifications may be generalized as follows:

Each pumparound: circul".tion rate Bnc! delta temperature (no change]

Condenser with vapor product: condenser temperature [no change]

Overhead liquid specification: D86 95 % distilled or top tray temperature

All liquid producIS except atmospheric gas oil: D86 95 % distilled ~

Specification for atmospheric gas oil/topped crude oil zone:


Overflash rate or
Gas oil draw temperature or
Gas oil 95 % distilled

Pumparound return temperature should never be specified since for this specification the
duty will only be correct when the simulated draw temperature exactly matches the plant.
Delta temperature should preferably be used for the specification to insure that the duty is
~orrect. Pumparound rale may be tuned as needed to match a pumparound return
lemperature for the model and the plant.
8 117

distillation specifications are better than TBP distillation specifications .for setting
1)1'<)(!uct rates. Simulated end points are not consistently accurate and the 95 % distilled.
. should be used in preference. The TBP distillation (or SiinOist) is very sensitive and not
as stable as the 086 distillation. The separation between atmospheric gas oil and topped
as
crude oil is sloppy, and a distillation specification may not be stable as the gas oil draw
temperat.ure. The model has maximum stability when an overflash specification is used
for this zone.

For each side product, a good model should have a reasonabLe match for the 5, 50, and 95
percent distilled and the draw temperature. The 5 percent distilled for a side product is
controlled by a side stripper and cannot be changed by tuning the main column. The 95
percent distilled for a side product is largely controlled by the draw rafe for the product
immediately below. Changing the internal reflux in the column has a much lesser effect.

The draw temperature for a side product is the bubble point of the side product. Recall
that the bubble point is the point at which the first trace ofvapor appears. Thus, the draw
temperature (bubble point) is affected by the composition of the side draw. To change
the dra"" temperature of a side product it is necessary to change the composition of the
side product. In a crude distillation column, the primary method to change the
composition of a side draw is to change the rate of the product below it. Note that
changing the draw tray location has 110 effect unless the composition is also changed by a
change in the product rates. To match draw temperatures it is also important that a
sufticient number of pseudo-components be available to represent the light components
in the draw.

A model should be tested for sensitivity. This may be done by selectively changing the
yields of the side products and observing the results. Oiscontinuities in the product draw
temperatures and laboratory distillations with rate changes are not realistic and indicate
that too few distributed components are available in the TBP distillation range for the
draw. A good model should behave like an operating column, in which the draw
temperatures and product compositions change in a gradual, continuous fashion.

Sometimes there are two products which are drawn in close proximity in the main
column; e.g., a light and heavy kerosene which are'drawn a few actual trays apart. For
proper simulation of this situation it is imperative that the number of pseudo-components
in the region of overlap for these products be increased substantially from the program
default value.
Crude Distillolion
118

References: . '
51 Nelson, W. L, "Regulation of 1. B. P. and E. P:, Oil & GasJ., p.143, (Aug. 25,

\945).
52 Twu, C. H., "An Internally Consistent Correlation for Predicting the Critical
Properties and Molecular Weights of Petroleum and Coal Tar Liquids", Fluid Phase
Equilibria, Vol. 16, pp.137-150 (1984).
53 "Molecular Weight of Heavy Petroleum Fractions", API Technical Data Book Figure
2B2,3, American Petroleum Institute, Washington, DC (1982).
54 Schneider, Donald F" "Select the Right Hydrocarbon Molecular Weight Correlation",
""
i
,~
Chem. Engr. Prog., pp. 40-44, (December \998).
d"

li
'I
1

',!",',1
,
1

I'
1:1
:1

L"

i'l
i'
;
I,
i
l'
I,
i
9.0
........,~.,.. Distillation

Vacuum distillation is a continuation of the crude oil distillation process. The topped
crude oil from the crude distillation column is heated in a furnace and distilled at sub-
atmospheric pressure to recover additional distillate and gas oil. The reduced pressure
allows extraction of these materials from the topped crude oil without using excessive
. temperatures and reduces the carryover of metals and carbon forming materials into the
gas oil product.

9.1
Vacuum Distillation: General Information
There are two types of vacuum distillation operations in refineries. The most common
operation extracts gas oil for charge to down-stream cracking units in the refinery where
it is converted to light gases and liquids, gasoline, and heating oil. The second type of
operation extracts petroleum cuts from the topped crude oil that are suitable for
production of lubricating oils. This process differs from gas oil production in that the
vacuum column has more in~emal reflux, and the side products are drawn to meet
specified viscosities and other related properties that are important for lubricating oils.
Not all topped crude oil is suitable for the production of lubricating oils. This chapter will
focus on vacuum units that extract gas oil for cracking units; however, many of the
principles also apply to vacuum units that make lubricating oil feed stocks.

For asphalt base crude oils, the vacuum column bottom product is used to make road
asphalt. For other types of crude oils, this material is usually charged to a coking
process, where it is destructively cracked to petroleum coke and low-grade gas oils. The
gas oils from the coking process must usually be treated to remove sulfur and nitrogen
before they are suitable for charge to cracking units.

9.1.1
Process Description
Vacuum distillation columns are normally designed to recover as much gas oil as
possible from topped crude oils. Metals and carbon forming materials are also distilled
into the gas oil and these set the limit for gas oil extraction. The TBP laboratory
distillation temperature that corresponds to the percentage of gas oil removed from the
topped crude oil is called the "cut-point" temperature. The cut-point temperature
depends on the metals and carbon formers (commonly designated "con-carbon" as
determined by the Conradson test) in the distilled gas oil. The cut-point cannot be
predicted with certainty and must be determined experimentally. It typically ranges from
WOO to 1125 degrees F (538 to 608 degrees C) for vacuum columns. Figure 9.1
Illustrates the product separations from a typical vacuum unit.

119
120 Vacuum UISUttu&'v"

Figure 9.1
Vacuum Unit Feed and Product TBP Distillations





;
"I'I' ,,, ,,
,,
;
,
I! , ,,
I:'
.11"


,,
J
I
"
,
,
,,
,
1,400 i---l----+-+--+-----+-----I--l+----+---1--
,,
,
,,
I-JF --I
v
'ii
il 1,200
,,

POin~:
,,
1/
,'I I Ligt t:" TE p Cut
V i-- _+1_ _

I-~-~\ ~~t _____ ~G___ --.!14 ___ J ____ _


ii Degrees F
,I L __
", J
'I 1,000 I_~ , I
1\ E /~ :,k~
"-
Vac um Resid

Ga Oi~

400L-~L-~--~---L--J---~~L-~~~--~

o 20 40 60 80 100
LV % Distilled

As can be seen in Figure 9,1, the TBI' cut-point between heavy gas oil and topped crude
is lower than the TBP end point for the heavy gas oiL The TBP cut-point represents the
temperature for a perfect separation between the heavy gas oil and the vacuum resid.
Note also that the maximum boiling point for components that distribute between these
two products is 1100 degrees F. This temperature represents about 29 LV percent of the
,i
9 121

""OUUlIIresid. Therefore, it is important that the TBP boiling point curve for the first 29
percent of the vacuum resid is accurate since these materials are in the separation
zone between heavy gas oil and vacuum resid.

Metals and carbon formers (con-carbon) tend to distribute in the products according to
the TBP boiling point of the oil; however, the distribution curves should be determined
analytically with a laboratory distillation and supplied to the simulator for predictive
purposes. An excellent paper has been published on the distribution of metals and con-
carbon in vacuum unit products by Golden and Martin".

The separation of interest in a vacuum unit in gas oil recovery mode is the separation
between vacuum resid and heavy gas oil. This separation takes place in the flash zone of
'. the column and is cOnlrol/ed by the flash zone pressure and temperature. The flash zone
pressure and temperature are determined by the flash vaporization characteristics of the
topped crude oil feed. .

Typical wet and dry vacuum unit operations are depicted in Figure 9.2. The operations
are similar except the wet unit uses steam to reduce the hydrocarbon partial pressure in
the flash zone to the desired level. The dry unit also has a boot cooler since the flash
zone is hotter than a wet unit for the same service. Both operations use steam ejectors to
produce a vacuum and both produce sour water that must be treated.
I1
Figure 9.2 shows the most common gas oil operation, where the light gas oil and heavy
gas oil are removed at total liquid draw trays. There is no reflux from the light gas oil
zone to the heavy gas oil zone and these products have a large overlap in boiling point
range as shown in Figure 9.1. For the columns in Figure 9.2, the wash grid exit liquid is
withdrawn from the column and recycled back through the furnace. Some vacuum units
route this liquid back to the column below the flash zone to mix with the resid. Others
send this liquid directly to tankage or another process unit.

The wet vacuum unit has a pre-condenser to remove excess water from the column
overhead prior to the ejectors. There is always a back pressure on the column overhead
equal to the vapor pressure of water at the condensing temperature il} the pre-condenser.
The total steam injected into the coil plus stripping zone is typically in the range 0[0.3 to
0.5 Ibsl gallon of vacuum resid (36 to 60 kgIM3).
i
I
The dry vacuum unit has a higher flash zone temperature than a wet vacuum unit for the
same service and it is generally necessary to provide a boot cooling circuit to keep the I,
column boot from coking and becoming plugged. The boot cooler subcools the liquid
from the flash zone and prevents coking.

Both types of unit have a wash grid above the flash zone. The feed to a vacuum column
enters the flash zone at very high velocity, and considerable heavy liquid is entrained in
the flash zone vapor. The heavy gas oil that is injected back into the column over the
wash grid washes down the entrained liquids. Metals and con-carbon are also washed
back in the grid. Golden and Martin" found that a well designed wet vacuum unit will
-E
122 Vacuum Distillation I
always produce the highest quality gas oil for any given cut-pOint. They also discuss a
third mode of operation called "damp" operation, in which coil steam only is used in the . .
vacuum unit. This operation has some of the benefits of a wet operation while not
requiring a pre-condenser to remove excess water prior to the ejectors.

Figure 9.2
Typical Vacuum Units

Pre-
Wet Vacuum Unit: Non-condensab(es Condenser
and steam
,--------.0---0{] High Pressure
Cooling Steam
Ught Gas Oil Water
Zon& L~-or1-c=.,.-<> Non-
4----'-_ Light c.w.
GBsOil
Heavy Gas Oil
Zone

Recycle Gc. Oil Yl:---~'-_"" Hea.,y SOU: Water

-1~~2==~~~:
Topped Wash Grid
Gas Oil
Crude Flash Zone

Feed
Coil
Stripping
Zone
o Ejectors

I
!
Steam Stripping

Steam
'-------<> Vacuum Re.id

Dry Vacuum Unit: Non-condensables


High Pressure
CW.
Steam

Ught Gas 0,1


" Non-condensables
Zone

Heavy Gas Oil


Zone
Recycle Gas Oil PIO-~-- Heavy ... Sour Water
Gas O~
Topped Wash Grid

Crud
J_~S1~===!i2:~~F/ash Zone
Feed Boot
o Ejectors
Coo/er
'-_.-1._ _ _-<> Vacuum Resid

.------.
123

Tvpic:al Operations and Control


The topped crude oil feeds to vacuum units have typical boiling ranges from heavy
kerosene (approximate boiling point = 500 degrees F = 260 C) through high boiling
residuum (boiling point = 1600 to 2000 degrees F= 871 to 1094 degrees C, depending on
the gravity of the crude oil). There are also some traces of dissolved light hydrocarbon
gas in the topped crude.

The overhead product from a vacuum column is comprised of light hydrocarbon gases,
nitrogen, oxygen, hydrogen sulfide, and light hydrocarbon liqutds commonly called
vacuum naphtha. The nitrogen and oxygen enter the overhead system through leaks.
However, most of the light hydrocarbon gases and vacuum naphtha are the result of
thermal cracking of the topped crude oil feed 'in the vacuum unit furnace.

Vacuum furnaces heat non-asphalt base topped crude oil to 720 to 770 degrees F (383 to
410 degrees C). Asphalt base topped crude oil is heated to 770 to 795 degrees F (410 to
424 degrees C). Injection of steam into the furnace coil increases the velocity of the oil
and reduces cracking; however, significant cracking still takes place. Non-asphalt base
topped crude oils crack more readily than asphalt base topped crude oils.

The furnace em uent is discharged through a large diameter transfer line into the vacuum'
column flash zone. The pressure drop across this line is in the range 2 to 5 psi (0.14 to
0.34 bars) and the temperature drop from the Joule-Thompson expansion into the column
flash zone is 15 to 30 degrees F (8.3 to 16.7 degrees C). Very high (sonic) velocities are
reached in the transfer line and subsequent distribution nozzle in the column flash zone. ,

According to Golden, et.al. 56 , these high velocities result in a non-equilibrium mixture of


I:
liquid and vapor being discharged into the flash zone, with substantial quantities of liquid 1
entrained in the vapor. .,I1
Superheated steam is injected into the stripping zone of wet columns and this lowers the 'I
bottom temperature 20 to 30 degrees F (i I to 16.7 degrees C) below the flash zone. I
Refiners like to keep the bottom temperature of vacuum columns below 700 degrees F 'i
I,',i
(371 degrees C) to prevent further cracking of the heavy oil and the resultant coke I
deposits in the bottom of the column. Therefore, wet vacuum columns that operate with
flash zones below 730 degrees F (388 degrees C) do not usuallyrequire boot coolers. On
the other hand, boot coolers are almost always required for dry vacuum columns since the
bottom produ;:t without cooling is at the flash zone temperature.

The operations depicted in Figure 9.2 have no reflux between the light gas oil and heavy
gas oil zones. Separation between these products is somewhat arbitrary and guided by
heat transfer considerations. (These products are often recombined and sent to a cracking
operation.) An old design rule is to remove at least twice as much heat from the heavy
gas oil zone as the light gas oil zone.
124 Vacuum Distillallon

Draw temperatures for the light gas oil are in the range 300 to 325 degrees F (149 to 163
degrees C) while draw temperatures for the heavy gas oil range from 500 to 575 degrees
F (260 to 302 degrees C). Newer designs cool the light gas oil with 'COoling water; many
older designs exchange light gas oil with cold crude oil and trim with cooling water. The
heavy gas oil may be used for at least two exchanges in the crude oil preheat train.

The vacuum column overhead temperature determines the <:arry over of oil into the
vacuum system. :'';ewer designs call for overhe3d temperatures of 150 degrees F (65.9
degrees C) or cooler, depending on the temperature of the cooling water available to the
light gas oil pumparound cooler. It is not uncommon to see overhead temperatures as
high as 275 degrees F (135 degrees C) for older units running at charge rates well above
design.

Figure 9.3
Vapor Pressures of Heavy Hydrocarbons
TEMPERATURE, DEG C
66 80 94 108 121 135 149

~'JO - 1 IDr , f' 1


150
400
100

50
30
/' V./ V./ 475
Q 20
V VJ' V/, "!)"
-'- ./ /' ./ ./
2 15 -/ )7 /f"'" /1 L 5?5
2_ 10
w
er
:J
en 5 ~~~ ./ -"" -"" / ./
" en / /' ~ 7 /' ./
w
er 3
"1'
V /" . / /" ./ V ./
[;7/vr7 /./V
Cl. 2 219
er
0 ?:>.:>.
Cl.
<{ 1
>0.7 ./ /' ./ ./
. <" ~

0.5 "7 "7


0.3 ."", ./ ./
0.2
/' V
274 V 288
1 0.1 I
125 150 175 200 225 250 275 300
TEMPERATURE, DEG F
9 125

chart for heavy hydrocarbons is shown in Figure 9.3 .. This chart may be used to
IStilnate the heaviest ,components in the vacuum naphtha as illustrated in Example 9.1

Example 9.1
Determine Vacuum Naphtha End Point

Case 1: A wet vacuum unit is operated with an overhead pressure of 60 mm Hg. The
mole fraction steam in the overhead is 0.95. Determine the end point of the vacuum
naphtha for overhead temperatures of I SO, 200, and 250 degrees F.

Solution: The partial pressure for the hydrocarbon = 60 (1.0 - 0.95) = 3.0 mm Hg
From Figure 9.3: Overhead, deg F . NBP, deg F .
150 415
200 483
250 540

Case 2: A dry vacuum umt IS operated with an overhead pressure of 10 mm Hg.


Determine the end point of the vacuum naphtha for overhead temperatures of 150, 200,
and 250 degrees F.

Solution: The partial pressure for the hydrocarbon = 10 mm Hg.


From Figure 9.3: Overhead, deg F NBP, deg F
ISO < 400
200 430
250 490

The flash zone pressure for vacuum columns is a critical design parameter that is based
on the vaporization curve for the topped crude oil feed and the type of operation; i.e.,
damp, wet, or dry. Dry vacuum units must run at lower flash zone pressures to achieve
the same vaporization as wet units. As Example 9.1 above illustrates, dry vacuum units
have less carry over of heavy hydrocarbons into the overhead system.

It is helpful to review design procedures to understand the selection of the flash zone
pressure for a 'vacuum unit. The flash vaporization curve for a topped crude oil is shown
in Figure 9.4. The TBP cut-point between vacuum residuum and heavy gas oil has been
determined in the laboratory to be 65.0 LV % which corresponds to 77.0 mole %
vaporized .into the overhead products. Observe from Figure 9.4 that the separation can be
made at the following flash zone operating points:
Pressure, mm Hg Temperature, deg F
20 690
30 712
40 730
50 745

.', .
126 Vacuum Distillation'

Since the crude is non-asphalt base it is desirable to keep the flash zone below 72S
degrees F. Therefore, an operating point of 3Smm Hg corresponding to 721 degrees F is
chosen. Example 9.2 illustrates selection of design flash zone conditions for a dry
vacuum unit and a wet vacuum unit to process this topped crude oil.

Figure 9.4
Flash Vaporization Curve for Topped Crude Oil
780
-,
770 ~Il!- loin! I
-:
760
750 1/ /
/ 1/1 I I If
I
,
740 / If 17
730 /1
/ /
/ I
'I I I
I "
/ 1/ J 1 I
LL 720 / /1 / f 17
-
tJl
(l) 710 ,, 1// / / ifi
1 I / 1/ J
~ I / / I I I
Cl 700 7
Q)
0 690 7
1// /
~. / / 1/ /
/
I "
rl
7 / / /
680 ./ / / / / 7 I
V If 1/ I I
i; 670 I j -/ 7 ~ I
7 V V / / (

,
660
650 ./
i
, ./
/"
,/
/"
'/ I
/
/ if -

I I
~,
IfU IoU pu :"W J~ I.tU
640
r-

III <11<1 II~ I
630
20 30 40 50 60 70 80
Mole Percent vaporized
Note: The topped crude oil composition has been modified to include cracked liquids alld
.gases produced in the vacuum furnace,

Example 9.2
Selecting Operating Point for Vacuum Column

"
Pro blem Description:
A vacuum column is desigr.ed to process the topped crude oil illustrated in Figure 9.4.
The flash zone conditions corresponding to the desired TBP cut-point between heavy gas
oil and 'vacuum resid are 35 mm Hg and 721 degrees F. Cooling water is available at 80

I
9 127

egrees F. A IO degree F approach may be assumed for the pre-condenser. The design
for the topped crude oil is 27,500 bbl/day. The rate of the furnace effiuent charge to
the column is 902 Ib moles! hour after correction for furnace cracking. At the design cut-
point, the rate of the vacuum resid is 27,500' 0.35 = 9625 bbl/day.

Case I: Select operating conditions for a dry vacuum unit to process the topped crude oil:

Solution: The flash zone must operate at 35 mm Hg for a dry vacuum unit. Assuming a
12 mm Hg pressure drop across the column, the overhead pressure is 23 mm Hg.
Assuming an additional pressure drop of 8 mm Hg across the overhead system to the I"
stage ejector, the pressure at the ejector must be 15 mm Hg. The column, overhead
system, and ejector system must be designed to meet these objectives.
'.

Case 1: Select operating conditions for a wet "acuum unit to process the topped crude oil.

Solution: The pre-condenser has a back pressure corresponding to the vapor pressure of
water at 90 degrees F. At 90 degrees F, the vapor pressure of water is 36 mm Hg.
Adding a safety margin of 5 mm Hg for the hydrocarbon partial pressure, the design
pressure at the pre-condenser is 41 mm Hg. Assuming additional pressure drops across
the overhead system and column of 8 and 12 mm Hg, the flash zone pressure is 41 + 8 +
12=61 mmHg.

The moles of hydrocarbon vapor in the flash zone is 902 * 0.77= 695 Ib moles! he. The
partial pressure for the hydrocarbon in the flash zone is 35 mm Hg. Solve for the total
moles in the flash zone:

(695/ Total FZ vapor) 61 = 35


Total FZ vapor = 695*61 /35 = 1211 Ib moles 1 hour

Steam in FZ = 1211 - 695 = 516 Ib moles! hour = 9,288 Ibsl hour

Steam is injected into the coil and into the stripping.section. Assuming 0.30 Ib steam!
gallon of resid in the stripping section:

Stripping steam, Ib/hr = (9625*42/24)*0.30 = 5 053

Coil steam, Ib/hr = 9,288 - 5,053 = 4.235

The tlash zone temperature tor the wet vacuum column will be approximately 10 degrees
F lower than the dry vacuum column because of the steam stripping of the vacuum resid.

A vacuum unit must be able to achieve the design flash zone pressure for good operation.
It is important that the pressure drop across the column to the flash zone be minimized
and many refiners have replaced trays with structured packing to take advantage of the
. lower pressure drop for packing.
128 Vacuum Distil/ation

The wash grid is always a packed section, and provides contact surface for washing of
heavy metals and con-carbon back into the recycle oil. It is important that enough heavy
gas oil is pumped back through the grid to prevent coking of heavy entrained materials
from the flash zone. The historic design wash rate has been 0.25 GPM of heavy gas oil I
ft2 of grid surface (061 M3! hr per square meter). c
Golden, et.al." have presented several cases where designs based on an equilibrium
c
separation in the flash zone have resulted in inadequate wash oil rates in the actual C
operations and premature shutdowns because of plugged wash grids. They present and
recommend a non-equilibrium flash zone model for use in column designs and.revamps.
Q
C
Occasionally, a rermer may configure a vacuum column with a packed bed between the
light gas oil and the heavy gas oil. This is illustrated in Figure 9.5. Hot light gas oil f
reflux is pumped back over this bed to improve the separation between light and heavy
gas oiL The light gas oil is drawn as a heavy diesei or heating oil for this arrangement.
C

Figure 9.5
,
4

Vacuum Column with Light Gas Oil Refiux


f
,--_,-_-,-_ _ _ High Pressure
Noncondensables ,
CW I
Steam
f

/'

Lioht Gas 011 C.W.


Non-condensables
~
/
Zone f--'-'+
il! I-'~,:J;:=--'-+ Light
... Gas Oil
/' C.w.
!Ii
L.i;}ht Gas 'JiE
Produ'.::t ~.
C
Wash Zone

,
if
il"
tl
OM Well A=mUiar Naphtha f
Ni Heavy Gas 0,1
HI Sour Water
Zone
I'"~ c
e-j~:~~:~~~~~~:.HeaVY
~
ii Recycle Gas Oil Gas OH
~,
Wash Grid
~i
Topped Crud
f ,I
o

Ejectors
Feed Boor
i1I Cooler
'------'----.Vacuum :;;sid
1:
if
I1 J
!l,
~
Similar to crude distillation columns, the size of vacU\.::-:: columns is determined by the
vapor loading. Vapor velocities are very high in vacuur.. ~olumns and range from 9 to 12
feet per second (2 75 to 3.66 meters per second).

:;!

Expansion options are more limited for vacuum units than for crude distillation units.
Unlike the crude distillation unit, the operational range for a vacuum unit is largely pre-
determined by the unit design parameters. Achievemem of the design separations at an
--------------------.-
9 129

i:lcPamled charge rate i~ dependent on the vacuum system being able to produce the
pressure in the flash zone. Increased charge rates not only put additional loads on
vacuum system, they also cause larger pressure drops across the column.

9.2
Vacuum Distillation Units: Simulation of Existing Columns
Most vacuum unit simulation models are developed for operational analysis and
bottleneck removal studies for existing operations; few new columns are being designed.
While the vacuum unit is relatively simple in principle, it is difficult to model accurately.
First, the feed stock includes the portion of the crude oil for which few laboratory data
are commqnly available. Laboratory work to supplement these known data is costly.
Second, operating data tend to be both scarce and inaccurate for vacuum units.

A step-wise approach to modeling vacuum units is presented in this section. In general,


the steps should be followed in the sequence in which they are presented. While the
techniques have been developed for modeling existing columns, many also apply to the
design of new columns. Some precautionary comments regarding new column design
and revamp studies have been included in the discussion.

9.2.1
Definition of the Topped Crude Oil
11 is imperative to have good representation of the topped crude oil charge. This almost
always requires additional laboratory work to define the true boiling point curve of the
topped crude oil. For accurate simulation results, the topped crude oil TBP curve must be
accurately defined for the heavy gas oill vacuum resid separation zone. The highest
temperature in this zone is the end point of the heavy gas oil and is typically 1050 to 1150
degrees F (566 to 521 degrees C). This temperature usually corresponds to the first 25 to
35 volume percent of the vacuum resid. Accurate representation of components boiling
higher than the heavy gas oil end point is desirable, but less important.

The default pseudo-component cut-point ranges in commercial simulators are inadequate


for models used for design and revamp. In the standard boiling point range 800 to 1200
degrees F (427 to (h9 degrees C), the pseudo-component cut-point range is defined as 50
degrees F (27.8 degrees C). Note that this boiling point range is nearly identical to the
heavy gas oil! vacuum resid separation zone temperature range. It is suggested that the
number of pseudo-components in this boiling point range be doubled. For vacuum
columns that make lubricating oil side-cuts, it is desirable to use 20 degree F (11.1 degree
Cl cut-point ranges for all components with normal boiling points lower than the heavy
gas oil end point temperature. See Section 4.1. 4 for more information on standard cut-
POint ranges.
-
130 Vacuum Distillation '

9.2.1.1
'I: Crude Assay Data
Data provided in typical crude oil assays are not adequate for definition of the topped,
crude oil charge to the vacuum unit The TBP distillation procedure has been discussed
in Seciion 3,1 2-od mea'.ures temperatures up to a maximum value of925 to 975 degrees F
(496 to 526 degrees C), depending on the composition of the crude oiL This does not
define the boiling points for many of the components :n the heavy gas oill vacuum res id
separation zone.

Methods to extend the TBP data for crude assays have been discussed in Sec/ion 8.2.1.1,
However, for accurate modeling of the topped crude oil, extrapolation by itself is not an
adequate solution, Extension of the crude oil, TBP through use of the D 1160 vacuum
distillation is, one plausible solution, since this test may be used to extend the TBP cUlVe
to temperatures of 1050 to 1125 degrees F (565,9 to 607.6 degrees C), depending on the
crude oil. This greatly reduces the uncertainty of the flash zone calculations.

Tb, high temperature simulated distillation (HTSD) measures temperatures up to 1332


degrees F (694,8 degrees C) "'ld is more accurate for cfLlde oil ,han the D:S37 simulated
distillation method (inaccurate for cmde oil), UnfOi1Unately, this procedure has a bias
toward paraffins and the simulated distiilation temperatures for high aromatic content and
asphaltic crude oils need corrections for temperatures above 500 degrees F (260 degrees
C). There are no standard corrections available, and corrections must be developed as
needed to match the yields and properties for the distillate and heavier products. This is
difficult to do for design purposes where no operating data are available for checking,

9.2.1.2
Topped Crude Oil Data from Product Blending
This technique has been previously discussed in Section 8.2.1.2. When data for the
vacuum unit products are available, it is the most reliable method to characterize the'
topped crude oil charge to the vacuum unit. The vacuum tower Gverhead stream is '
comprised mostly of light liquids and gases created by cracking in the furnace. These,
materials are estimated and added to the furnace effluent in the simulation model.

The light vacuum gas oil may be accurately analyzed with standard laboratory tests.
normal boiling point range of the heavy vacuum gas oil extends to approximately 1100
degrees F (593.7 degrees C) and may be measured with a DI160 vacuum distillation or a
D2887-e>.'tended simulated distillation. (The D 1160 is more accurate for high aromatic
and asphalt base crude oil). At least a partial distillation can often be measured .
these tests for the vacuum resid. Recall that it is not necessary to have an .c,-urate
boiling point curve for the vacuum resid at temperatures above the end point of the
gas oil. This usually occurs in the first 25 to 35 volume percent of the vacuum resid.
simple vacuum unit flash zone model illustrated in Figure 8,13 may be used to. ,n__ ~colnciile
131

~\bl,en(led
topped crude oil produced by blending of the vacuum unit products with the
plant operation. _

Sometimes no laboratory distillation data are available for the vacuum resid. A
procedure for fabrication of a vacuum resid laboratory distillation is given in Example
8.5. This procedure is limited to the simulation of existing columns.

9.2.1.3
Molecular Weight Estimation
Commercial simulators estimate the molecular weight of a pseudo-component from its
average normal boiling point and average gravity. For a given boiling point and gravity,
the molecular weight is also a function of the composition, a parameter not well
represented by the open literature methods Used in a commercial simulator. When
molecular weight information is available for the topped crude oil, it should be supplied
and used in preference to the estimated values from the simulator.

Molecular weight is an important property for vacuum unit calcula,ions since vacuum
units are vapor loaded and the molecular weights of the pseudo-components have a direct
eITect on the vapor volume. A good comparison of open literature molecular weight
methods for vacuum column calculations has been published by Schneider".

The generalized method ofTwu" predicts reasonable molecular weights for most refming
processes. This method and others are available in commercial simulators. The 1980
API Extended '-.1ethod" predicts the highest molecular weights of all open literature
methods and hence predicts lower column loading than the other methods. For design
and revamp calculations, a more conservative method is suggested.

9.2.2
Adjustments to the Topped Crude Oil
There is always somp cracking of the topped crude oil in the vacuunl furnace to light
gases and petroleum liquids. These materials go overhead in the vacuum column and are
removed by the vacuum ejector system. According to Nelson", the amount of non-
condensable gas that must be removed per 1,000 barrels per day of charge stock ranges
from 15 to 50 pounds (1.0 to 3.5 kg! M3 charge stock). It consists of gas dissolved in the
feed stock, ligh! materials created by cracking in the furnace, and a tail of low boiling
material inhere", from the crude oil fractionation. It is necessary to add these materials to
the topped crude oi! to properly model the top of the vacuum column. An accurate
estimate for these materials is not needed for simulation of existing columns. However,
for design and revamp calculations, the estimate is important since it affects the sizing of
the ejector system.

are some old rules_oJ thumb that. may be used to estimate the topped crude oil
.a(lJIUStm,ents. For revamps, some effort should be made to collect some actual data for the
13T vacuum UISlIIIUUUfI

topped crude oil being processed, since cracking is a function of the composition as well
as the furnace temperature.

Dissolved light gases: Ibs/hr gas = 11.5 *( bbls/day feedl I 000)

Note that this adjustmelll is not necessary whell the topped en/de oil is generated by
simulation 0/ the crude distillation unit.

Cracking gases: IbS/hr gas = Cl * (bbls/day feed/24)


where: Flash Zone
Cl deg F deg C
1.2 800 427
0.6 775 413
0.3 750 399
0.15 725 385
0.08 700 371

Front end tail (native):


Ibs!hr = 50 (bbls/day feed/lOOO) {typic,~! 0.5 LV % tail}

Note that this adjustmelll is not necessary when the topped en/de oil is generated by
simulation a/the crude distillation uflit.

Front end tail (cracking):


Ibs/hr = C2 * (bbls/day feedll 000)
where: Flash Zone
C2 degF degC
67 800 427
35 775 413
20 750 399
12 725 385
5 700 371
Air leaks into the overhead system:
Ibs/ hr = 6.0 * (bbls/day feedi 1000) \,
,
,
u'
i: ,
The above relationships are not elegant, but give reasonable results. Since these
i materialsmllst be handled by the ejector system, better estimation procedures should be
used for design and revamps.

The non-condensable gas product from the ejector system is comprised of H2, H2S, CO,
!! '
;: '
CO" N" 02, methane, ethane and propane plus materials. Interestingly, the molecular
weight is always about 30.0. For simulation purposes, the dissoked and cracking gas
may be represented with a 751 25 mixture of ethane and propane. The air leaks may be
ii'

11
ii

I
llL
9 133

~re:sented with nitrogen, and the front end tail material may be modeled as a 50150
;;;':.""I-e of normal undecane and normal dodecane.

The hot topped crude oil feed from the vacuum unit furnace should be adjusted prior to
;;.-.,'he vacuum column calculations.To maintain a mass balance in the flow sheet, the
weight of the various adjustments (except the air leaks) should be subtracted from the
weight of the topped crude oil. These adjustments are small compared to the topped
crude oil flow, and they may be spread evenly over the unadjusted topped crude oil
boiling point range. Example 9.3 illustrates use of the above estimation procedures.

Example 9.3
Adjustment of Topped Crude Oil Composition'

Problem Description:
50,000 barrelslday of topped crude oil are charged to a vacuum unit. The vacuum
column operates' at a temperature of 725 degrees F in the flash zone. Adjust the topped
crude oil composition as needed for the vacuum column calculations.

Case 1: The topped crude oil is prepared by simulation of the crude distillation unit.

Solulion:
Since the topped crude oil has been prepared by simulation of the crude distillation unit,
il is not necessary to add dissolved gases and native liquid tail material. Necessary
adjustments are for cracking and air leaks and are calculated as follows:

Cracking gas = 0.15 (50,000/24) = 313 Ibsl hr


Liquid tail from cracking = 12 (50,0001 1000) = 600 Ibsl hr
Air leaks = 6.0 (50,000/1000)"2 = 42 Ibs! hr

The mass of the topped crude oil is decreased by 913 Ibs!hr. The cracking gas, liquid tail,
and air leaks are added to the topped crude oil to produce the adjusted charge to the
column. Nole that the air leaks actually enter through the column~o\'erhead system:
however. it is cOfH'enientto add this small adjustment to the columnfeed.

Case 2: The topped crude oil is prepared by blending the vacuum unit products.

Solution:
Two additional adjustments are needed versus Case I. They are calculated as shown
below and included with the adjustments determined for Case I.

Dissolved gas = 11.5 (50,0001 1000) = 575 Ibsl hr


Native liquid tail = 50 (50,000/1000) = 2500 Ibsl hr (assuming 0.5 LV % lail)

.'
134 Vacuum Distillation

9.2.3
Collection of Operating and Laboratory Data
Data for vacuum columns are not as accurate as data from crude distillation columns
because of the nature of the materials being processed. Flow rates are more difficult to
meter accurately for the topped crude oil feed and the resid streams. Few data are
collected if ever for the vacuum overhead streams, i.e., the non-condensable gases and
the vacuum naphtha drained from the hot well accumulator. As mentioned in Section
9.2.2, some data for the overhead products are necessary for the simulation model and
must be estimated when not known. Laboratory distillations are often not run for the
light and heavy gas oil since the control parameter is usually the calor and metals content
of the heavy gas oil and there 'is no control on the light gas oil.

The following operating data should be collected'when possible:

-Topped crude oil charge rate to the column


- Steam rates to the coil and stripping WIle for wet units
- Rates for all products leaving the column (overhead products are a bonus)
- Rates for a\1 pt;mparound stren!,:, (net and total)
- Rates for all pumparound cooling streams
- Pressures:
Column overllead
Flash zone
Bottoms (not critical)
Ejectors (when modeling the vacuum system)
- Temperatures: '
Column overhead
Product draw trays
Furnace inlet and transfer temperature
Column flash zone
I Column bottom product
Return streams for all pumparounds
I.; Inlet and exit temperatures for all pumparound cooling streams
I Vacuum system temperatures (when modeling vacuum system)

,
The following laboratory data are recommended:
, !

- Topped crude oil data or sufficient product data to construct the topped crude
oil as described in Section 9,2.1.2.
- Lab distillation and gravity for light. and heavy gas oil
- Gravity for the vacuum resid
- A partial distillation for the vacuum resid
i! - D86 distillation and gravity for vacuum naphtha (a bonus)
I, - Component breakdown for the non-condensable vapor (a bonus)

l
f~;.:.,...
I


135

... feed stock and product rates and gravities should be used to check the unit material
:ballanc:e before the model building is begun. If the material balance is in error by more
than five weight percent, the source of the imbalance should be located and corrected.

For wet vacuum units it is necessary to have accurate flow rates for the coil steam and the
stripping steam. There are no simple guidelines for estimation of the column steam
floWS. Questionable or inaccurate steam flows also add another degree of difficulty to
reconciliation of the separation and temperature in the flash zone of the column. When it
is necessary to reconcile the flash zone data, the simplified flash zone models presented
in Figure 8.13 are useful.

It is useful to check the pumparound exchanger data. Usually there is no vaporization of


the cooling medium (crude oil or cooling water) and heat transfer is all sensible heat
Example 8.6 illustrates verification of pumparound data. For vacuum columns, the
following specific heats may be assumed: ligh'tgas oil = 0.60 btu/ Ib-deg F (2.51 kj/ kg-
deg C), heavy gas oil = 0.63 btu/ Ib-deg F (2.64 kj/ kg-deg C), and vacuum resid = 0.65
btullb-deg F (2.72 kjf kg-deg C)

It is sometimes dimcult to reconcile the temperature drop from the furnace to the flash
zone of the vacuum column. The drop for the transfer line only should be in the range IS
to 30 degrees F (83 to 16.7 degrees C). This corresponds to 3 to 4 psi (0.21 to 0.28 bars)
of pressure drop. Dry vacuum units tend to have somewhat greater temperature drops
across the transfer line than wet vacuum units. When the temperature drop is higher than
the above range, the pressure drop across the furnace transfer line should be checked. If
it is found to be 5 psi (0.34 bars) or less, there is most likely leakage from the wash grid
collection pan (slop wax collector) down into the flash zone.

Draw temperatures for the light and heavy gas oils mayor may not be accurate,
depending on the point of measurement. The pumparound data may also be used to
check the accuracy of the draw temperatures for the light and heavy gas oil. In particular,
it is easy to check the light gas oil draw for newer designs since cooling water is used in
the pumparound exchangers and cooling water rates may be measured accurately.
~

The bottom product from a wet column with steam stripping will be 15 to 30 degrees F.
{B.3 to 16.7 degrees C) cooler than the flash zone. For columns with boot coolers, it is not
unusual for the resid pumparound rate to be inaccurate. Therefore reconciliation of the
boot cooler rate is best accomplished by assuming that the pumparound delta temperature
IS correct.

9.2.4
Translation of Actual Configuration to Theoretical trays
All column simulation models are based on theoretical trays. For a theoretical tray there
is perfect mixing, and the liquid and vapor leave the tray in perfect liquid/ vapor phase
tqllliliibri' Because of the high vapor velocities and low liquid levels on vacuum-
,",

136 Vacuum Distillation


.-
column trays, there are few theoretical trays in an actual column. It is also true that
vacuum columns with packed sections perform very little separation and packed sections'
(or trayed sections) seove more as direct contact heat exchangers than as fractionation.
devices.

The vacuum column is similar tothe crude column in that all of the heat is introduced in
the feed. Separat:o~ is mosr!y rectification of heavy materials, except for wet columns
with resid stripping zones. The light and heavy gas oil zones are refluxed internally with
the material condensed in the zones by the pumparound coolers. There is usually no light
gas oil reflux to the heavy gas oil zone and the two gas oil zones operate independently.
Unlike the crude distillation column, there is no external reflux to the top of the column.

Fewer than ten equilibrium trays are required to model any wet or dry vacuum unit with
two side products. Similar to the crude distillation column, the yield of products is
primarily a function of the composition of the feed stock, not the degree offractionation.
The number of trays have little influence on the boiling point range for the side products.
Rather, the end point for any side product is regulated by changing the rate of the next
lower product.

Th.; tray elTiciency models provided in commercial simulatOrs are not valid for vacuum
distillation and should not be used. The translation of the column c():lfiguration to
theoretical trays should be done by the model builder, with the resultant theoretical trays
supplied to the simulator program. The translation 10 theoretical trays for the various
zones in a vacuum column is discussed below.

9.2.4.1
Steam Stripping Zone for Wet Vacuum Units
One theoretical tray is adequate to represent steam stripping of the vacuum resid.

9.2.4.2
U Boot Cooler Circuits
I

These may occur on both wet and dry vacuum columns. A portion of the resid bottoms is
cooled and circulated back to the boot of the column to cool the vacuum resid product
leaving the stripping zone or flash zone. This inhibits cracking and the resultant coke
deposits in the bottom of the column. There are usually no trays or packing in this
,
, cooling loop and the purpose of the boot cooler is to subcool the resid product to a
temperature less than 700 degrees F (3 7l A degrees C). The bottom of the column (the

I: :1
boot) acts as a heat transfer device and produces no vapoL

It is convenient 10 include the boot cooler as a part of the distillation model for the
I. , I vacuum column. This may be accomplished by using a theoretical tray to represent the
,i bottom of the column and feeding a small amount of non-condensable inert gas to this
uay to produce a vapor product. The subcooled tray may now be solved as a part-of the
9 IJ1

acuum column. Figure 9.6 illustrates models for wet and dry column boot coolers. It is
lc.onvc:ni,~nt to use the inert gas estimated for column leaks (nitrogen) as the inert gas feed
.to the subcooler tray.

Figure 9.6
Modeling Boot Coolers for Wet and Dry Vacuum Columns

Dry Vacuum Column:


Actual Configuration: Simulation Configuration:

Feed
) Aash Zone -'--H Flash Zone

Boot
Boot Cooler
Cooler

Resid
Resid

Wet Vacuum Column:


Actual Configuration: Simulation Configuration:

Feed Flash Zone


) Flash Zone -i-I
Steam Stn"pping Zone

Steam Boot
Cooler
Boot
Cooler

Resid Resid

9.2.4.3
Light Gas Oil Zone
The light gas oil zone consists of the reduced diameter section of the column from the top
of the heavy gas oil section to the top of the vacuum column (entry to overhead line).
This section functions as a condenser for gas oil not condensed in the heavy gas oil zone.
For most vacuum columns, all of the light gas oil is withdrawn from the bottom of this
zone and there is no light gas oil reflux to the heavy gas oil zone. Two theoretical trays
Usually suffice for this section of the column. The bottom tray represents the light gas oil
draw tray and the top tray represents the light gas oil pumparound return tray.
OccaSionally, an additional tray between the draw and return trays gives better agreement
with the plant operation.
138 Vacuum Di!.till'ati.-.

For vacuum columns with light gas oil reflux to the heavy gas oil zone as depicted
Figure 9.S, an additional tray below the light gas oil draw tray is satisfactory t~ represent
the rectification from the light gas oil reflux. .

9.2.4.4
Heavy Gas Oil Zone

The hea\'j' gas oil zone is the region of the column between the wash grid zone and the
light gas oil zone. This section is at the maximum diameter of the column and works
mainly as a condensing zone for heavy gas oil. Two trays are usually sufficient to
represent this zone, with the bottom tray being the heavy gas oil draw tray and the top
tray being the heavy gas oil pumparound return tray.

In the actual column, al\ heavy gas oil is withdrawn at the draw tray and sent to the heavy
gas oil pump. A metered portion of the pump discharge is directed back into the vacuum
column over the wash grid. The quantity of wash oil is a critical operating parameter and
too little wash will result in coking of the wash grid und shutcown of the column For
simulation purpuses, the wash oil is represented as the net tray liquid ftl'w leaving the
heavy gas oil draw tray as shown in Figure 9.7.

9.2.4.5
Wash Grid and Flash Zone
For designs and revamps, it is critical that this zone be modeled conservatively. In this
respect, the modified flash zone representation suggested by Golden, et al. >t', should be
considered. This model is believed to guarantee enough wash oil flow to ti,e wash grid to
prevent coking. For simulation of existing columns it is not nc~essary
,, sophisticated flash zone model and an equilibrium separation may be assumed.
;i "

I:"
,.

f'
I"i ,
il!
,1:,1
Figure 9.7
IIeavy Gas Oil Zone

I Actual Configuration: Simulation Configuration:

ii j',i
ii
il
,

, "i
~1
~~~,.--11-+
Tt . VVash Oil
'-',', ',j I- ~ Heavy Gas 011 't------'~.... Heavy Gas Oil
~
;,
i
Wash Gn"d Wash Oil
~~;j Wash Gn'd
139

is wise to use a simplified flash zone model such as those presented in Figure 8.13 to
. reconcile the flash zone 'conditions and the vacuum resid yield before attempting to
model the complete vacuum column. Flash zone modeling problems are usually caused
by poor representation of the topped crude oil, but they may also be caused by poor
operating data or mechanical problems. Resolving these problems prior to undertaking
the full column model can save many hours of frustration.

The liquid leaving the wash grid is collected and withdrawn from the column. It is highly
. contaminated with metals and concarbon and is given a nomer such as "slop wax" or
"dirty gas oil". There are three cases to consider when modeling the wash grid and flash
zone as depicted in Figure 9.8. The first case recycles the slop wax back to the furnace.
The "second case injects the slop wax into the bottom. of the vacuum column with the
vacuum resid, and the third case sends the slop wax to tankage Or another process unit.

Figure 9.8
Treatment of Slop Wax

Case 1: Recycle Slop Wax. Case 2: Rejoject Slop Wax Case 3: Remove Slop Wax
Heavy Gas OH Heavy Gas Oil
Heavy Gas Oil

Slop Wax Wash Gn"d Slop Wax


Wash Gdd
Flash Zone
Stn"pping
l--{:J--L~-'/ Flash Zone FI8sh Zone
Stripping
Steam Zone Zone

Steam .Resid Steam Resid Steam Resid

o Note: For dry VaCuum columns, Case 2 injects slop wax into the boot.

a
Historically, the typical vacuum column has 3 to 6 feet (914 to 1829 mm) of wash grid
which 'performs as no more than one theoretical tray. At least two theoretical trays are
recommended for representation of the wash grid to better represent the vaporization of
wash oi I that takes place in the wash grid zone. This does not guarantee a wash oil rate
satisfactory for design or revamp studies, but it does force the model to use more wash oil
to maintain a desired wash outlet from the wash grid which is more true to the actual
operation. A theoretical tray is also used to model the slop wax collector tray.
I
For an operating column the slop wax is not a true measure of the overflash. In addition
to overflash it contains heavy materials entrained in the flash zone vapors and materials :\
that condense on the bottom of the heavy gas oil draw pan and fall back onto the wash 11
. grid. An equilibrium flash zone model predicts no entrainment, and the equilibrium tray
model for the heavy gas oil draw pan does not predict under-tray condensation. Golden,
e!.al." present some techniques for determining the true overflash for operating vacuum
columns.
140 Vacuum Distillation

Figure 9.9
Simulation Models for Wash Grid! Flash Zone

Case 1: Recycle Slop Wax. Case 2: Reinject Slop Wax Case 3: Remove Slop Wax

Hvy Gas Oil Hvy Gas Oil HI/y Gas 01\


Vl/ash Oil 6 Wash Oil 6 Wash Osl 6

IWBsh Gnd
Steam
Slop Wax

~
Slop Wax I.....,_-~Slop

-i.--'f'f--oj -''-1EC: Heel Wax


Input

L.._ _ _ I.
Resid
Steam
Resid
Steam
Resid

Notes: Theoretical trays are shown for all models.


11 denotos a true flo'.vsheet recycle 10T 'Case 2.

A small n:'! flow of stop wax is specifted in


Case 2 and Case 3 fOI calculation p:..lrposes.

{,
The simulation models corresponding to the three slop wax arrangements are shown in
Figure 9.9. Note that the flash zone is represented as a theoretical tray in these models.
This may be accomplished in a simulator by using a theoretical tra\". or by using a "feed
flash" option which separates the feed into vapor and liquid portions. For the feed flash
option the liquid is fed to the designated feed tray and the vapor is fed to the next tray up
(the slop wax collector tray). Observe for Case I that the rec;cle of slop wax to the
furnace is modeled internally as a net tray liquid flow to the Hash zone tray. The feed
tray heater adds the incremental heat needed to bring the slop oil to the flash zone
temperature. This shortcut model gives equivalent results to one in which the slop wax is
removed from the column and recycled through the furnace with the topped crude charge.

9.2.5 -
;:~

"
Solution Techniques: Insidei Out Algorithm
The Inside/ Out column algorithm (U 0) is well suited to solve vacuum column problems.
The vacuum column appears deceptively simple, but it can t;e a difficult problem to solve
with a commercial simulator. Problems with column convergence arc usually caused by
conf1icting performance specifications or by poor estimating procedures within the
simulator of use. Problems in matching the actual operation are caused by poor
representation of the feed to the column, inaccurate operating data, and/ or mechanical
problems with the actual column such as leaking seal pans, etc.
9 141

U 0 algorithm is an iterative method that must have an initial starting point. Data
. supplied by the model builder include the column pressure profile and estimates for the
column temperature and flow profiles. The pressure profile is not changed during the
solution process. For the U 0 method, good flow profiles are not as important as good
temperature profiles for speeding the convergence process. However, even though the
uo algorithm is similar in principle among the commercial simulators, some simulators
are definitely superior to others in the internal set-up and convergence of vacuum
columns. Therefore it is good practice to provide reasonable estimates for the column
temperature and flow profiles.

The pressures supplied by the model builder are unchanged during solution. Pressure
profiles across vacuum columns are non-linear, and key pressure measurement points
should be furnished. The flash zone pressure should always be supplied, either directly
as a pressure for a theoretical tray representing the flash zone, or indirectly by supplying
pressl'fes for the slop wax draw pan and the tray immediately below the flash zone.

Temperature estimation is simple for a vacuum column. The following points are
recommended: top of column, light gas oil draw, heavy gas oil draw, slop wax draw,
flash zone, top stripping tray (wet columns), and the bottom of the column.

Flows should be estimated for all products for which the flow is not a perfomlance
specification. The overhead flow estimate is important and should equal the non-
condensable gases and steam (for wet columns only).

9.2.5.2
Initial Model Building Phase
It is important to reconcile the flash zone yields before attempting to model the complete
column. After this step has been completed, it may still be a struggle to converge the
complete column model. As Previously mentioned, difficulties always lie with the
performance specifications and! or with the poor solution techniques used in the column
algorithm. (Vacuum columns have regions of low liquid flow and this causes
convergence problems for some of the commercial simulators.) The simplified model
presented in Figure 9.10 may be used to overcome both of these problems. The
functional relationships in the column are easily understood and the model produces high
quality flow profiles to use as estimates for the complete column model.
-
142 Vacuum Distillation

Figure 9.10
Simplified Vacuum Column Model

Actual Configuration: Simulation Configuration:


Non-condensables
and steam

Ught Gas
11
(I
Lj---,-.. Ughl
Gas 01 Heavy Gas
Gas Oil r
Slop Wax 011 Zone Heavy
-t":
..\
Re~CYcle T,.nsl.,~a:: [ Gas Oil <I

Slop VVax Heavy line Slop wax


Gas Oil Feed 0 -
I-:~~J
n_L:Q=~,---'! Stripping Zones ,I,
Feed
-1 Furnace - Steam
Steam I
I--....
Vacuum Res;d
'f

Steam
Vacuum Hesid Note: Theoretical trays are shown.
Steam
Assume slop wax TaP is last 70 % of H'.y Gas Oil TEP.
Assume slop wax AP1 = Hvy Gas Oil API 6.0
;:-

The simplified model presented in Figure 9.10 divides the vacuum column into three
smaller columns. The only simplification in this model versus a complete column model
is that the slop wax recycle is not converged. This has little effeCl on the ans\\'cr and for
"quick and dirty" analysis the slop wax recycle estimate may be omitted from the model.

, ,
1-:
Observe in Figure 9.10 that it is not possible to change the vacuum resid yield without a
change in either the steam flows or the furnace transfer temperature. Steam flows are not
generally used as tuning parameters at this stage of model building. Therefpre, to change
the vacuum resid yield it is necessary to add more heat to the feed to increase the t]ash
z.one temperature. Note that a heat source could be added to tray 1 of the column
j representing the flash and stripping z.ones as a convenient way to tune the flash zone
I: temperature. This additional degree of freedom allows specification of the rate for the
vacuum resid.

The second column in the simplified model represents the heavy gas oil zone, wash grid,
and slop wax draw tray. It is obvious from this model that the wash oil (net heavy gas oil
from tray 2) and the slop wax now from tray 5 are not independent of one another. One
or the other of these two flows may be specifted, but not both. Specification of the slop
wax flow is always a solvable problem and the wash oil will seek the necessary level.
Note that when the wash oil flow is specified, the flow must be large enough to guarantee
a flow of slop wax from the bottom of the column.
Joml'ter 9 143 -

heavy gas oil draw rate is controlled by the vapors condensed by the 'pumparound
cooler. Therefore, to specify both the pumparound cooling duty and the h.eavy gas oil
draw rate is an overspecification since these parameters are directly related. Observe also
that the heavy gas oil draw temperature is another way to specify the heavy gas oil rate.
However, this specification may not always be possible to meet since the heavy gas oil
draw temperature is affected rather significantly by the vacuum resid flow. (The slop
wax is a small flow versus the heavy gas oil and not a good tuning parameter for the
heavy gas oil draw temperature).

The third column serves as the final condenser for gas oil. The temperature of the
overhead is controlled by the pumparound cooler. The light gas oil rate is not a
reasonable specification, since this rate has already been determined by the withdrawarof
the heavy gas oil product in the preceding column. Neither is the light gas oil draw
temperature a good specification since it can.only be changed by changing the flow of the
i
heavy gas oil product in the second column. . 'I
,I
For this simplified model (and the complete model also) it is generally best to specify the
rates for the light and heavy gas oil pumparounds and allow the delta temperature (duty)
to be calculated. To specify both the rate and delta temperature for one of these
pumparounds is equivalent to specifying the rate for the corresponding gas oil product.

The simplified model is easy to solve with any commercial simulator since there are no
small internal liquid flows in any of the three columns. The calculated flows may be
supplied as estimates for a one column model to speed the convergence process.

Figure 9.11 presents a one column model for the vacuum column discussed above. This
column has two pinch points in the internal liquid profile. These occur at the light gas oil
draw tray and the slop wax draw tray where the actual column internal flows are zero.
Zero internal flows are not solvable in distillation algorithms and a small internal flow
must be specified to solve the model.

The rationale from the simple model may be used to select appropriate specifications for
the one column model. Since the flash zone temperature cannot be changed by this
model, the resid flow should not be specified. (Adding a. trim heater to tray 8 would
allow the resid flow to be specifIed). Very small net liquid flows are specified for trays 2
and 7 to simulate the total withdrawal of liquid from the column at these trays. The
heavy gas oil rumpback of wash oil is modeled as the net liquid flow from tray 4.
-

~:,'
144 Vacuum Distillation

pre?
Figure 9.11 spe,'.,!
One Column Model flo;"
req:'"
Actual Configuration: . Simulation Configuration:
!
9.;f
NOfHX)ndensabies
and steam
Non-oond:;"1sables + S:~2:n

Tt',
'. 2
No!
Light Light 510<4
GasOU
NetFJow
L GasOit fee",
;(
tod
. Net Row 4
'diw1
Is-- Heavy f

Heavy Steam
WashGrid ,C
, 6 Gas011
It i~f"
Slop VVax
Gas Oil

oJ_~_i~.--l
-l
1\ Net Ro..... 7 rela!;;

!F-.::.aee
Steam
Steam Vacuum Resid
Feed
1\;\

F'umac6
Tr.nsfer Jne

0-
Sl~am
i8lI pro
oil

' - - _ - : -_ _..Vacuum
Slop Wax Resid

Notes: Theoretical trays are shown.


11 denotes a true now sheet recycle.

Either the slop wax draw rate or the wash oil rate may be speciEed, but not both.
SpeciEcation of the slop wax draw rate is always solvable; therefore, this flow is chosen
for a speciflcation.

The overhead temperature is specifled, with the light gas oil pumparound duty allowed to
seek the necessary level to satisfy this specification. The heavy gas oil produet draw rate
may be speciEed and the heavy gas oil pump around duty allowed to seek the level to
meet this rate. The rates for the light and heavy gas oil pumparounds are specified and
the corresponding delta temperatures (duties) are calculated. This completes deEnition of
the column performance specifications.

No;e Ihal some alternate specifications are available. The wash oil rate could be
speciEed instead of the slop wax rate. The light gas oil draw temperature or light gas oil
rate could be specified instead of the heavy gas oil rate. It may be possible to substitute
the heavy ".3S oil draw temperature for the heavy gas oil rate; however, this speciEcation
may not solve since it is also dependent on the resid now. (Note that a trim heater on tray
8 allows the heavy gas oil draw temperature to be specified instead of the resid rate.)
9 145

column illustrated in Figure 9.11 does not have a boot Cooler. When a boot cooler is
the subcooled bottom temperature (subcooler tray temperature) should be
, and the cooling duty calculated at a sPecified resid pumparound rate. Resid
. flows are notoriously inaccurate, and the resid pump'!round flow rate may be tuned as
required to match the observed delta temperature in the plant.

9.2.5.3
Tuning the Model
No amount of tuning can account for poor representation of the topped crude oil feed
Slock. . As previously discussed, a standard crude assay TBP is inadequate to represent the
feed to the vacuum unit. Therefore when a crude distillation model is used to produce the
lopped crude oil feed, the crude oil data must be tuned prior to simulation of the crude
distillation column. .

It is not uncommon for vacuum columns to have mechanical damage. A good working
relationship with the plant operations personnel is invaluable in understanding these
problems. Sometimes the draw pans develop leaks. A leaking draw pan for the light gas
oil is manifest as a lower draw temperature for the heavy gas oil, with reduced heat
recovery in the heavy gas oH pumparound exchangers.

A leaking collector tray for the heavy gas oil results in a decrease in the heavy gas oil
product rate, and a cooling of the flash zone temperature from the increased slop wax
recycle. The temperature of the slop wax collector tray is also reduced. A leaking slop
wax tray results in a direct cooling of the flash zone and decrease in gas oil extraction.
Note that leaking pans may be modeled by increasing the draw tray lIet liquid flows.

There should be a reasonable delta temperature between the slop wax collector pan and
the flash zone. If there is not, there is probably substantial entrainment of heavy material
from the flash zone vapor. These hot, heavy materials are being condensed in the wash
grid and vaporizing most of the wash oil before it comes through the grid. The wash grid
may well be coking in the middle and the unit heading for an unschedul;d shut-down.

It is not always apparent where the furnace transfer temperature was measured.
Temperatures measured ahead of the actual transfer line are higher than the temperature I

8t the entrance to the transfer line. Depending on the efficiency of the furnace, !

temperatures prior to the transfer line may be significantly higher than the transfer line
entrance. If the temperature drop from t:ie furnace transfer to the column flash zone is \
il
larger than 30 degrees F (16.7 degrees C). the pressure drop across the transfer line
should be checked. If this pressure drop is less than 5 psi (.34 bars), either the transfer I
temperature measurement is prior to the expansion into the transfer line Or there is
leakage of slop wax into the column flash zone.
1.
Ij
specifications other than rates are desirable for generalization of models.
slop wax in a si mulation rr.odel is the true everf1ash and may be specified as a ratio II
I
:,
1"\
,j;
1
!III
ill. I.
~I I
III".i,
1I
rnT~ - '--, --.

Vacuum Distillation
146
instead of an absolute rate. As previously mentioned, the slop wax rate measured in the
plant operation. should be corrected for underpan condensation and heavy liquid
entrainment in the flash zone vapor. These corrections have been discussed by Golden, .
et.al."
The 9S .percent distilled for the heavy gas oil may be specified when the flash zone
te::1Ferature is tuned with a trim hc~ter. This specification is equivalent to a specification
for the flash zone temperature or the resid flow.

,
'!

i:
!!!
~i

:1
9
]47

55 Golden, Scott, and Martin, Gary, "Revamping Vacuum Units for HVGO Quality and
. Cutpoint". Paper AM-91-4S. 1991 NPRAAnnual Meeting, March 17-19, 1991.

56 Golden, Scott W., Martin, Gary R., and Villalanti, Dan C., "Feed Characterization and
Deepcut Vacuum Columns: Simulation and Design". Paper 47a. 1994 A.I.Ch.E. Spring
National Meeting, April 18-20, 1994.

57 Nelson. W L., Oi/GasJ., p.IOO, (ApriIS, 1951).

58 Golden, Scott, Lieberman, N.P., and Lieberman. E.T., "Troubleshoot Vacuum


Columns with Low-capital Methods". Hydrocarbon Processing. pp 81-89; (July 1993).

I
1I

1:1

il
:1
I
I'i'
,
'ilr,
1:1"I
~j
I
....

Chapter 10

Ii
,
"
j
Refinery Reaction Systems
Petroleu m refineries have many reaction processes. The cracking processes are the
oldest, with the thermal decomposition of petroleum reported by Si II iman S9 in 1871.
The oldest cracking processes were based on thermally cracking the oil into smaller

I
lower-boiling IW': ":-,, les, especially those in the gasoline boiling range. While the
thermal processes were successfui in increasing the gasoline production from crude oii,
, the\' also produced light gases high in sulfur, heavy tar-like materials, and carbonaceous
I
!, deposits which necessitated periodic shut-down and clean out of the cracking furnaces
I:
il and drums.

Most of the reactor systems in rcflOeries today use a catalyst to promote a desired
rearr2ngement of the petroleum molecules. The catalytic cracking process has largely
replaced thermal cracking and is considered to be the heart of the modern refinery. The
process is continuous, with the catalyst constantly regenerated to a fresh reactive state.
Not only does it produce the most gasoline of the catalytic processes, it also produces
light hydroc:lrbons suitable fOf building high octane gasoline with ancillary processes.

Ir ;'ecent ,C'us, the use of catalytic Iwdrocracking has in,';'eased in rdineries. This
p,'ocess uscs 3 high hydrogen environment and severe conditions to crack the more
refractory gas oils to gasoline and light distillates. It is used as a compznion process to
catJI,1ic cracking which takes the more easily Clacked paraffinic gas oils from crude and
\'2cuum distillation units. Both cracking processes have substantial volumetric gains in
pr,'~~lct versus feed, further enhancing the economic benefit to the refinery..

O:',;;:r rcacti0n processes are used to rebuild light hydrocarbons and to convert the
he:l\'icst poniun of the petroleum into salable products. The goal for all of the refinery
reactors is the same: upgrade the feed stock into products of higher value ana increase the
prufitability of the refinery.

10.1
Reactor Processes: General Information

.-\ bc:ef overview of the various refinery reactor processes is given in this section. There
:.:e ::lultiple licensers of the processes in this section and variations in the reactor details,
,'~e:2ting conditions, and the process flow sheets. However, the process goals and the
o:er.c'3i operating strategies are nearly transparent tram licenser to licenser. SpecifiC
I
I ,,,2c:~r details and operating conditions arc licenser proprietary information, and all
cni,xfllmioll ill (his book is gelleric and I/O/ 5pecific 10 al/y [icel/sed process.

Reac:c'f processes may be grouped into several categories: catalytic cracking,


h\'dre,cracking and hydrotreating, reforming and isomerization, alkylation and
poi\'rnerization, thermal and coking, hydrogen production, and petrochemical production.

-,
;1
If 148

il
1'1.\.'.

------... _--_ -_ .. ....


10 149

;ev~~ral general types of reaction occur in these p'rocesses: cracking, dehydrogenation


isomerization, cyclization (decydization), alkylation (dealkylation),
'oondensation (polymerization), coking, and treating (sulfur and nitrogen removal).
Cracking reactions break molecules into smaller molecules by removing side chains and
by breaking the basic molecular structure into multiple parts. Dehydrogenation reactions
release hydrogen atoms from molecules to form unsaturated compounds such as olefins
and aromatics. Hydrogenation reactions saturate olefins and aromatics with hydrogen,
Isomerization produces highly branched isomers from "straight chain" molecules.

The cyclization reactions form new ring structures while the decyclization reactions open
ring structures. Alkylation reactions combine smaller molecules into larger molecules.
Condensation (polymerization) reactions grow molecules by combining simpler
structures. Coking reactions convert some of the feed stock to an elemental carbon form
which is deposited on the reaction catalyst and! or a receiver vessel such as a coke drum,

Usually, more than one type of reaction occurs in a given type of refinery reactor. For
example, all of the reaction types mentioned above occur to some extent in the catalytic
cracking process, even though the cracking reactions predominate. Some polymerization
takes place in alkylation reactors, resulting in formation of heavy polymer materials that
must be removed from the product. Even a simple reaction system such as an
isomerization unit may have a small amount of cracking taking place because of the high
hydrogen environment in the reactor.

A brief discussion of the various refinery reactor systems is given below,

Footnote:

Throughout this chapter the following shorthand notation is used for the various classes
of h yd rocarbons:

Hydrocarbon Class Shorthand Notation


Paraffin (alkane) P r

Olefin (alkene) o
I Ring Naphthene (cycloparaffin) N
Cyclo-olefin CO
1 Ring Aromatic A
2 Ring Naphthene 2N
2 Ring Aromatic 2A
3 Ring Naphthene 3N
3 Ring Aromatic 3A
4 Ring Naphthene 4N
4 Ring Aromatic 4A
5 Ring Naphthene 5N
5 Ring Aromatic 5A
---
150 Refinery Reactor

10.1.1
Catalytic Cracking

Figure 10.1
Catalytic Cracking Process
Lig ht Gases
Lift G2S
i
Reactor Effluent
C3s. C4's
I ProduCt . Gasoline
Separation
Reactor I'ght Cycle Oil
Gas Oil
t,, Stripping Steam
~
Decant Oil
,, Zone

,,, l...-catalyst + Coke


,, V Heavy Cycle Oil
, Flue Gas
r--T-~
,,
,,, Reger.E;3tor I ,,
,,
,
- Air
,
,,,
,, 1 ,
Reg. Catalyst
: Heavy Cycle Oil (recycle) I
I __ ~ ___ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

General Information:
Figure 10.1 presents a block flow diagram for tbe catalytic cracking p; llceS5. Gas oil
I: (optionally) recycle oil are mixed with hot, regenerated catalyst and transported to
reactor. The reactions take place on the catalyst, with a carbonaceous material
1111

1 1,1' deposited on the catalyst. The "spent" catalyst is stripped with steam to remove the
_I'!: and circulated back to the regenerator. Air is blown into the regenerator and the
i: burned from the catalyst. The catalyst also has some sulfur deposits which are oxidiZll
,:
r to S02 in the regenerator. The catalyst cycle is repeated and so on.
I' . \ '.
li
,i!
The fluid catalytic cracker (FeC) is the predominant type of unit in operation today.
the Fee, the catalyst is in the form of very fine particles that will fluidize with a
Ti,e injection of lift gas containing a small amount of H2S into the standpipe (riser)
gaining popularity as a method to reduce the poisoning effect of metals in the feed

For newer Fee designs, most of the reaction actually occurs in the riser which tranSj:1C!
th,~ mi;,.-ture of catalyst and oil vapor to the reactor bed. This is known as "riser
and the reactor serves more as a disengaging device for the reacted vapor and the
MIl.ler J 0 151

Older FCC units were designed to bum the reaction coke to CO. Newer designs bum the
reaction coke to either a mixture of CO and CO2 or completely to CO2 . The regeneration
reactions are exothermic and a substantial amount of the heat is transferred to the
regenerated catalyst. The heat from the catalyst supplies the bulk of the heat needed to
vaporize the liquid feed (and recycle if present), to raise the temperature of dispersion
steam to the reactor, and provide the overall endothermic heat of reaction.

The reactor effiuent is separated into light gases, C3's and C4's, C5 plus gasoline, light
cycle oil with ASTM 086 end point < 700 F (371 C), heavy cycle oil (optional product),
and decant oil with TBP end point up to 1200 F (649 C). Heavy cycle oil is an optional
product that is sometimes pulled from the main fractionating column. It may be used to
control the separation between light cycle oil and decant oit It is sometimes recycled
back to the reactor to lower the API gravity of the decant oil.

The C3 and C4 product from the cat cracker isrich in propylene and butylenes and may
be used for petrochemical operations or for the production of additional gasoline through
polymerization and/ or alkylation units. The C5 plus gasoline is also rich in light olefins.
Because of environmental concerns, some refiners are using other reaction processes to
react and remove the C5 olefins from the gasoline. The cracking reactions also produce
aromatic compounds in the gasoline boiling range which are high in octane.

Process Conditions:
The cat cracker reactor is a low pressure, high temperature operation. Reactor pressures
typically are in the range 20 to 35 psig (2.4 to 3.42 bars), with a small pressure
differential maintained between the reactor and the regenerator. The main fractionator
operates at a small pressure differential from the reactor outlet.

Cat cracker reactors operate within the temperature range 0[900 to 1025 degrees F (483
to 552 degrees C), and regenerators reach temperatures from 1150 to 1500 degrees F (621
to 816 degrees C). The higher regenerator temperatures are for cracking of residual
materials where two stages of regeneration must be used with special metallurgy in the
regenerator internals to burn the additional coke production.

The severity of a cat cracking operation is measured by conversion where:

Conversion, % = 100 (volume fresh feed- volume cycle stock) / vOlu'me fresh feed
and cycle stock = light cycle oil + net heavy cycle oil (if any) + decant oil

Typical cat cracking conversions are in the range 65 to 85 percent.

Reactions:
Two types of catalyst are used in cat cracking processes: silica-alumina, and zeolites on a
low silica/high alumina matrix. Most units today use the newer zeolite catalysts because
of the more favorable product distribution. Because of the higher activity of the zeolite
catalyst, the residence time of the oil in the reactor may be reduced.
-
152 Refillery Reactor Systems

Cat cracking catalysts are poisoned by nitrogen, sufur, and metals, i.c., iron, copper, 1
nickel, and vanadium. rhe nitrogen and sulfur form compounds' that reduce the number e
of active sites on the catalyst and the metals deposit on the catalyst and promote a
undesirable reactions. In particular, the metals promote production of e," gas (H 2 ) and F
coke formation.
J
The gas :,il feed to a catalytic cracker contains dozens of actual com;onents of many
c~,(;mical classes. Because of the many types of reaction that taKe place. the numb", of' J
,
" reactions that occur can number in the thousands. It is impossible to cc:?letely analyzc
the gas oil feed to a catalytic cracker and model the reactions. A brief b: of some typical
reactions is given in Table 10. I below.

Table 10.1
Typical Reactions in Cat Cracking Reactol'S

Cracking Reactions:
Pn ~Pm + On-rn
On ~Om + On-m
!'-'n <:::!">Nm + On-m
Cr"..
"..." ~ (Om + On-l~l
.-.. . r. <:0:> An: + On-m (side ClUB us)
(2~)n ~ (2N}m + On-m (side Ch:Il11S)
(2A)n <:0:> (2A)m + On-m (side chains)

Isomerization Reactions:
nPn "'" i-Pn
,,On"'" iOn

/):!h,vdroge!latfon ReoCliofls:
p 00>0 +El
o W P + A
CO "'" A + 2H2
N W (2N) + H2 (eyclization)

Condensalion Reactions:
2 An c:> (3A)2n + 3 H2
An + (2A)111 w (~A)n+m + 3 H2
.A.n + (3A)m CO (5A )n+m + 3 H2

Cl,'clization Reaction1i:
o CO N

Coking Renc[(ons:
-" CO Coke + H2
2-" cc' Coke + H2
3...... C::"> Cokc+H2
153

heat of reaction for all of the various. reactions taking place is slightly
~hermlc. It varies somewhat with the severity of the operation, the type of catalyst,
the comPosition of the gas oil feed. Sadeghbeigi60 reports that the heat of reaction for
s can range from 120 to 220 BTU/ Ib (279 to 511 kj/ kg).

ng and Hydrotreating
Both of these reactors are catalytic and both use a high hydrogen environment to treat the
feed stock. In the hydrocracking reactor, the operating conditions are severe, and the
strategy is to crack the feed stock into lighter products and to saturate olefinic and
aromatic compounds with hydrogen. Sulfur and nitrogen are converted to hydrogen
sulfide and ammonia and removed in the reactor. The chemical hydrogen consumption is
high for the hydrocracking process, and a refinery must have an additional source of
hydrogen available from that normally produced by the other process units. The most
common supplemental source is a hydrogen generating plant that steam reforms natural
gas.

Hydrotreating is a mild form of hydrocracking. The strategy in hydrotreating is to


remove sulfur and nitrogen and to saturate olefinic and some aromatic compounds in the
feed stock. Cracking is not desirable since the treated feed is usually a finished product.
Hydrogen consumption is much lower for hydrotreating and most refineries have
sufficient hydrogen available from the catalytic reforming process.

10.1.2.1
Hydrocracking
General Information:
The catalytic hydrocracking process predates catalytic cracking. The process was
invented in Germany prior to 1930 and brought to the United States by Esso Research
and Engineering Company. There was little commercial use of the process until the
1980's, when low values for fuel oil products and environmental demands for clean fuels
made it economic to upgrade low-grade fuel oils to more salable products.

Hydrocracking is unquestionably the most flexible cracking process and it is used in a


wide range of applications. In fact, it is often possible to vary the process conditions
significantly on a ~ingle unit to process a variety of feed stocks. This process
complements catalytic cracking by cracking the more refractory cycle oils from thermal
operations. It is sometimes used to upgrade the cycle oils from catalytic cracking to
lighter products.

A typical hydrocracking proces5 flowsheet is shown in Figure 10.2. Gas oil feed is
combined with recycle hydrogen, heated by exchange with the reactor product followed
by a furnac.e, .. and fed to a reactor bed. The net heat of reaction is exothermic, and the
c

I Refinery ReaclOr '>y')I""'~,


I reacted mixture is cooled by injection of quench hydrogen prior to entering a second '

I
I:
I]
reactor bed. The resultant product from the second reactor bed is cooled by exchange
with the feed and sent to a series of separators where the liquid products are removed
from the unreacted hydrogen and light gases. A water wash is used to remove some of
the impurities from the hydrogen recycle stream. An amine treating process removes any
remaining ammonia and hydrogen sulfide from the recycle gas prior to re-circulation to
the process, Fresh hydrogen is added to the system as needed to replace the hydrogen
consumed in reaction and to maimain a desired level of hydrogen in the recycle gas.

Figure 10.2
Hydrocracking Process

Fresh H2
Purge
Recycle Gas
H2

Reactors Compressor
NH3, H2S
Quench
H2
Wash
Bed 1 H20

,--____ Off Gas


Oil
Low Pr-es.
Feed
Cold
peparator

.I:' .'.
,I Separa:or

j
ii,
i,~

i,
i' '
I' The flowsheet in Figure 10,2 has been simplified. Hydrocracking processes may have
d multiple trains of reactor beds; however, the principle is the same, and quench hydrogen
;/
is injected between the reactor beds to control the reaction temperature. Depending on
the process and the feed stock, there may also be a "guard" reactor prior to the
hydrocracking reactor(s) to remove catalyst poisons and improve the product distribution
and catalyst life for the hydro cracking reactor(s).

Hydrocracking reactors have fixed beds of catalyst that must be taken off-line from time
to time for regeneration of the catalyst and/ or catalyst replacement. The run cycle is
I
dependent on the feed stock being processed and the severity of the operating conditions:
, '
Catalyst may be regenerated several times before replacement is necessary.

L
10 155

Conditions:
PrclceliS conditions vary widely for hydrocrackers because of the variety of feed stocks
Ihat are processed. There is a relatively large amount of hydrogen that is consumed, and
it is usually necessary for a refinery with hydrocracking to have a supplemental source of
fresh hydrogen, such as a hydrogen plant.

Reactor operating pressures range from 1000 to 2000 psig (70 to 139 bars), depending on
the process and the feed stock. Temperatures are in the range 600 to 850 degrees F (316
to 455 degrees C). The reaction temperature is controlled between reaction beds with
quench hydrogen.

Hydrogen consumption is a function of the feed stock being cracked and the severity of
the operating conditions. It may run ariywhere from 500 to 3000 SCFI barrel charge (89
to 534 SCMI M3). The various processes call for a hydrogen to feed hydrocarbon ratio
of 1500 to 4000 SCFI barrel (270 to 712 SCMI M3) entering the .reactor.

Cracking feed stocks include diesel fuel, atmospheric and vacuum gas oils, FCC cycle
oils, coker cycle oils, and residual oils. Cracked feed stocks contain higher
concentrations of unsaturated compounds than virgin products and have higher
consumptions of hydrogen in the reactor. A key reaction in the hydrocracker is the
hydrogen saturation and conversion of aromatic rings into naphthene rings that may be
cracked. Aromatic rings are very stable and cannot be cracked with standard catalytic
cracking processes.

Hydrogen saturation of olefins and aromatics results in a substantial volumetric increase,


and liquid volume gains of up to 25 percent are not unusual for hydrocrackers. This
process also produces less propane and dry gas than the other cracking processes.
Saturation of feed olefins and olefins produced by cracking is very rapid and complete.
Depending on the feed stock and the operating severity, significant saturation of aromatic
rings may also be accomplished.

Reactions:
Hydrocracking catalysts are a crystalline mixture of silica-alumina (early cat cracking
catalyst) with a small uniformly-distributed quantity of a rare earth metal within the
crystalli"ne lattice structure. Rare earth metals most commonly used are platinum,
palladium, tungsten, and nickel. The silica-alumina portion of the catalyst promotes
cracking reactions, 'while the rare-earth metals promote hydrogenation reactions. These
reactions are complementary, with the exothermic hydrogenation reactions providing
reaction heat for the endothermic cracking reactions. Hydrocracking catalysts are
susceptible to poisoning by metalic salts, oxygen, organic nitrogen compounds, and
sulfur in the feed stock,

Guard reactors typically use a catalyst of cobalt-molybdenum on silica-alumina to


remove sulfur and nitrogen compounds and to protect the precious metals in the
hydrocracking catalyst. For hydrocracking of heavily contaminated feeds, such as
156 Refinery Reactor Systems .

residual materials, it is necessary to use guard reactors to prolong the hydrocracking


catalyst life and maintain the desired product distribution.

The gas oil feed to a hydrocracker may have dozens of actual components from several
chemical classes. The many combinations of cracking and hydrogenation reactions result
in hundreds of reactions occurring. Table 10.2 gives a brief list of some of the typical
reactions that occur in the hydrocracker reactor.

Table 10.2
Typical Reactions in Bydrocracker Reactors 'cl

l(vdrocrocking (Cracking + Hydrogenation) Reactions:


Pn + H2 ~ Pm + Pn-m
On +2H2 ~ Pm + Pn-m
Nn + H2 ~ .Nm + Pn-m (side chain removal)
An + H2 ~ Am + Pn-m (side cluin removal)
il (2N)n + H2 ~ (2N)m + Pn-m
(2 ..... )n + 1-12 <:::> (2A)m + Pn-m
(side chain removal)
(side chain removal)
y (3~!n + H2 ~ (3N)m + Pn-m (side ch.ain removal)
11,
(3A :1. + 11.2 <:::' (3N)m + Pn-m (side: ci::lin rcmoy;: I}
'L
!.f
:I:i Note: Olefins formed by cracking ure instantly satW"3ted ",nh hydrogen.

f someriza/ion Reactions:
n-Pn ~ i~
n-On <:0:> i-On

H.',:drogenalion Reactions:
On + H2 ~ Pn
,-\.n + 3H2 co Nn
(2N)n + H2 ~ Nn (ring opening)
['
I (2A)n + SH2 <:0:> (2N)n
(2A)n + 3H2 <:0:> An (ring opening)
(3N)n + H2 <:0:> (2N)n (ring opening)
11
11
(3A)n + 3H2 ~ (2A)n (ring opening)
:i
Condensation Reactions:
An + Am ~ (3A)n+m + 3H2
An + (2A)m <:0:> (4A)n+m + 3H2
An + (3A)m ~ (5A)n+m + 3H2

,")esul!urizmion and DenilrUicafion:


s + H2 co H2S
2 Nitrogen + 3H2 co 2 NH3

Feed olcfins and olefins created in the reactor are rapidly saturated in the high hydrogen
atmosphere. Isomerization is also favored in the reactor and high octane isoparaffins are
present in the reactor product. Condensed aromatic rings are also saturateo-to
10 157

/ClC)pllfaffills that may be cracked to smaller molecules. There are no unsaturated non-
structures in the reactor effluent. Hydrogen sulfide tends to inhibit the saturation of
atC,mllllc rings. This conserves hydrogen and produces a gasoline of higher octane than a
. straight naphthenic gasoline.

The overall reaction provides an excess of heat because the amount of heat released by
the exothermic hydrogenation reactions far exceeds the heat required for the endothermic
cracking reactions. This excess heat causes the reactor temperature to rise and
accelerates the reaction rate. This is controlled by the injectior. of cold hydrogen quench
into the reactors to absorb the excess reaction heat.

10.1.2.2
Hydrotreating

Figure 10.3
IIydrotreating Process

Recycle hydrogen Compressor Purge gas

Makeup
H2

Reactor
Water
Wash

Feed Cold ..
Separator
Furnace

Feed! effluent To
Exchange '----_ _ _ _ _- - ' L - _ Fractionation

General Information:
A typical hydrotreating process is shown in Figure 10.3. The process is similar to
hydrocracking but differs in two respects: reactor conditions are mild to inhibit cracking
reactions, and the process is only mildly exothermic and does not require quench cooling
of the reacted mixture.

Hydrotreating has been in general usage much longer than hydrocracking. The simplest
type of hydrotreater is the naphtha desulfurizer reactor which precedes the naphtha
reformer. Hydrotreaters are also used to "polish" distillate fuels by removing sulfur and
nitrogen and saturating olefinic materials that cause thermal instability. Some aromatic
158 RefineryReactor Syslel1f~ ,

saturation may also be accomplished. and this is important when treating kerosene
boiling range materials to raise the smoke point and meet jet fuel specifications. It may
also be desirable to pretreat a catalytic cracker feed to reduce the sulfur and nitrogen
content and improve the distribution and quality of the cat cracked products. The guard
reactor for a hydrocracking process is in reality a hydrotreating reactor (See Section
10.1.2.1.)
T:
In the process, the oil feed is mixed with the recycle hydrogen and preheated by exchange T:
wit:, the reactor outlet. A furnace is used to bring the feed to the desired reaction
temperature. The reactor effluent is cooled and the liquid products removed and sent to
fractionation. The recycle hydrogen is treated in an amine treater to remove HIS and
recycled to the process. Fresh hydrogen is introduced to make up the hydrogen
consumption and solubility losses. It is also necessary to purge some recycle hydrogen to
control the hydrogen content of the recycle gas to the reactor.

Process Conditions:
Process conditio[ls vary, depending on the feed stock. Conditions are milder than
hydrocracking since i. is undesirable to crack the feed stock. Typical reactor pressures
are in ;hc range 500 to 1000 psig (35.5 to 70 bars) and temperatures range from 550 to
700 d'cgrees F (288 to 371 degrees C).

Hydrogen consumption is much lower than for hydrocracking and ranges from 100 to
500 SCFI barrel of charge (18 to 89 SCMI M3). The unsaturated compounds in cracked
stocks make hydrogen consumption higher than that consumed when treating virgin J
stocks. There is usually sufficient hydrogen available from other process units such as
the naphtha reformer(s) to meet this requirement.

The hydrogen to j,j'drocarbon ratio it: the reactor feed varies froil~ 500 to 1500 SCFI
barrel of fresh charge (89 to 267 SCMI M3), depending on the stock being treated.
Higher hydrogen recycle ratios are used for ctacked stocks than for virgin stocks to
enhance the saturation reactions for olefins and aromatics.

There is usually a small loss in treated product volume versus the feed because of light
cracking. This is somewhat offset by the volume .gains from saturating olefins and
aromatics.

Reactions:
Hydrotreater catalysts are typically bi-metallic, such as cobalt-molybdenum or nickel-
molybdenum on an alumina structure. The catalyst is placed in a fixed bed arid must be
periodically regenerated and! or replaced. The critical operating variable is the hydrogen
partial pressure in the reactor. Because of hydrogen consumption within the reactor, the
hydrogen partial pressure can drop significantly at the reactor outlet.

The feed stock to a hydrotreater is often a more narrow boiling range material than that to
a hydrocracker. There are still a substantial number of actual components present.
because of the large number of components in pel,oleum based stock:;. -. The number
10 159

i!8CtIOI1S taking place is fewer than the hydrocracker, and may be numbered in the
dozens versus the hundreds of reactions' in the hydrocracker. Some of the typical
reactions are listed in Table \0.3.

Table 10.3
Typical Reactions in Ryd rotreater Reactors j,
I:
J

Hydrocracking(Cracking + Hydrogenation) Reactions: \


. Pn + H2 ~ Pm + Pn-m
On + 2H2~ Pm + Pn-m !
(
Note: Olefins fonned by cracking are saturated with hydrogen instantly. I
I
I
Hydrogenation Reactions: .
On +H2~Pn
(2A)n + 3H2 ~ An
(2A)n + 5H2 ~ (2N)n
(3A)n + 3H2 ~ (2A)n
(4A)n + 3H2 ~ (3A)n
(3A )n + 7H2 ~ (3N)n

Note: saturation of I ring aromatics is negligible.

D~s;ulfllri:nlion and Denilrijicalion:


S +H2 ~ H2S
2 Nitrogen + 3H2 ~ 2 NB]

McCulloch and Roedef' report that almost no single ring aromatic saturation takes place
at normal hydrotreating conditions, but there can be appreciable poly-aromatics
saturation. They also report that olefin and diolefin saturation is essentially complete and
almost no cracking takes place under normal treating conditions. These authors also
present methods to estimate chemical hydrogen consumption and calculate the hydrogen
panial pressure at the reactor outlet. r '

Cooper, et.al!' present experimental aromatics saturation data for several gas oil samples
when hydrotreated. Several catalysts were investigated over a typical range of reactor
temperatures and pressures. Aromatics saturation was found to reach a maximum value
with reactor temperature for any given pressure level and then decline. The greatest
degree of saturation 'occurred for two and three ring aromatics.

Gary and Handwerk6J report that the typical heat of reaction for hydrotreating reactors
used in preparation of hydrocracker feeds is 25,000 to 35,000 Btu per barrel (\66 to 232
MJ/ M3) of raw feed.

I'i
."-.~---~

160 Refinery Reactor Systems


Ch
10.1.3 Gt
Reforming and Isomerization Tb
Th
Reforming and isomerization are processes that are used 10 rebuild hydrocarbons. These co
processes are designed to alter the chemical nature of a gasoline feed stock such that the co
1S
OCtane number is increased. Cracking is not a desired reaction, since it decreases the
yield ofhigh~octane gasoline and increases the production of light gases ~nd coke. At
of
Both processes use a high partial pressure of hydrogen in the reactor to promote
isomerization reactions and to reduce the depositation of carbon on the catalyst (coking). TI
The naphtha reformer catalyst also promotes the cyclization of paraffins into naphthenes, re
and the dehydrogenation of naphthenes into aromatics. The resultant aromatic sI
compounds have much higher octanes than the feed stock paraffins and naphthenes. T
However, because the aromatic compounds are denser than the corresponding paraffins
2.nd naphthenes, there is a volumetric shrink in a reformer. h
SI
11
Both processes use a fixed bed of catalyst that must be periodically regenerated; however,
in recent years a continuous catalyst rege:1cration process (CeR) has been developed and c
v
irr:;c:emented for th(c catalytic reformer.

10.1.3.1
Catalytic Refor~ing
Figure lOA
\' aphtha Reforming Process
Net hydrogen
,\
Compressor
r-______________________~O~r-----~R~e~C~y~d~e~h~y~d~ro~g~e~n~----~

3rd
Reactor

Heater
Heater Heater
Separator
Heavy -----f:y---'
Naphtha
L TO
Stabilizer
10 161

edenl Information:
catalytic reforlning process came into common usage in refineries in the late 1940's.
are three variations of the process in use today: semi-regenerative, cyclic, and
':co,ntinuou:s1y regenerative (CCR). The semi-regenerative process is the oldest and
co,nsllsts of mUltiple fixed catalyst beds (usually three) in series. For this process, the unit
is operated until the catalyst has deactivated to a point where regeneration is necessary.
AI this point, the unit is taken off stream and the reactor beds are regenerated by burning
the coke deposits and then treated chemically to restore activity .

. ,: The cyclic process is similar to the semi-regenerative process except that an additional
-".,c:, reactor
(swing reactor) is incorporated into the unit. The swing reactor is brought on
stream as it is necessary to take one of the other reactors off stream for regeneration.
Thus, the reactors are regenerated one at a time while the unit stays on-stream.

In the continuous regenerative process, the catalyst is circulated through the reactors in
somewhat similar fashion to the catalytic cracking process. The catalyst circulation loop
includes a regeneration step where the coke is burned off the catalyst and the catalyst is
chemically treated prior to returning to the reactors. It is obvious that the cyclic process
will have a more constJ.nt product yield structure than the semi-regenerative process.
Furthermore, the continuous process will have a more constant product yield structure
than the cyclic process because of the more constant level of catalyst activity.

Figure 10.4 presents a typical flow sheet for a non-regenerative process. The heavy
naphtha feed is combined with recycle hydrogen and preheated by exchange with the hot
reactor effluent from the last reactor. The preheated naphtha! hydrogen feed is brought to
the desired inlet temperature for the first reactor in the main furnace. The effluent from
the first reactor is re-heated to the desired inlet temperature for the second reactor in the
first inter-heater and so forth. The mixture of product and light gases from the last
reactor is cooled and separated into hydrogen-rich gas and the liquid products. A portion
of the hydrogen-rich gas is withdrawn from the unit to maintain a hydrogen balance, and
the remai nd er is recycled back to the first reactor.

The naphtha reformer is used to upgrade a significant portion of the cr!lde oil from a low
octane heavy naphtha (gasoline) that is unsuitable for motor gasoline into a high octane
gasoline blending component. It is also used to produce aromatics (especially benzene)
for petrochemical processes. A by-product of reforming is a relatively high hydrogen
COntent net gas stream that may be used in hydrotreating and hydrocracking operations.

Operating Conditions:
The feed stock to the naphtha reformer is usually a straight run (virgin) naphtha from the
crude distillation process. Hydrocarbons with fewer than six carbon atoms produce no
useful products when reformed, but tend to hydrocrack to light hydrocarbon gases while
. reducing the capacity of the unit to process good reforming stocks. Therefore, only the
heaviest portion of the naphtha from crude oil distillation is selected for reformer feed.
,
162 Refinery Reactor Systems

The ASTM DS6 distillation for a gasoline operation is usually kept somewhere in the
range IS5 to 3S5 degrees F (S5 to 196 degrees C). Depending on the severity of the
operating conditions, there is an end point rise of 15 to 30 degrees F (S.3 to 16.7 degrees
C) for the reformed gasoline product (reformate) versus the feed stock. Heavier stocks
not only raise the end point of the reformate product, they also hydrocrack more readily
and lower the catalyst activity by producing more coke.

When a reformer is being used to produce aromatics for petrochemical operations, the
end point of the naphtha is reduced somewhat, and the process conditions are altered 10
selectively promote the fonnation of aromatic compounds. Often, a refiner may have one
reformer dedicated to producing aromatics and the. other (s) producing blending stock for
motor gasoline.

The endothermic dehydrogenation reactions that predominate in the reformer result in


significant temperature drops across the reactors. To keep the reaction rates high, inter-
heaters are used between the reactor beds to reheat the reactor effiuent to the desired inlet
temper2ture. The inter-heaters may be sep3rate furnaces, or separate coils within a large
furn::cc. The temperature drops across the reaction beds progressively decrease as
exot:.c. mic reactions suo h as iSC':'lerizatiol' ""d hydrocracking begin to occur after the
firs! ; "action bed. A scmi-regellcrative th"ee reactor process such as Figure 10..; may
have typical temperature drops of 90 to 130 degrees F (50 to 72.2 degI~es C), 40 to 60
degrees F (22.2 to 33.3 degrees C), and 10 to 20 degrees F (5.6 to 11.1 degrees Cl across
the three reactor beds.

For the classic semi-regenerative process, the temperature drop across the last reactor is
monitored to measure catalyst activity. This reactor will have a small temperature drop
when the catalyst is fresh. which gradually increases as the catalyst deactivates and the
exothermic hydrocracking reactions increa:,C',. It \\lay eventu~lly become a slight
temperature rise as the catalyst becomes deactivated.

Usually, a refiner will operate the refonner with identical inlet temperatures to all
reactors. Typical inlet temperatures are in the range 915 to 980 degrees F (491 to 527
degrees C).

There is a fairly wide range of pressures for refornler operations, and the process may be
operated in the range 100 to 500 psig (7.9 to 35.5 bars). Lower pressures favor aromatics
production and isomerization. Higher pressur~s ravor hydrocracking.

The hydrogen to hydrocarbon ratio entering the reactors is another control variable. For
gasoline operation, a ratio from 3 to 5 mols hydrogen per Olole hydrocarbon is commonly
used.

The naphtha charge to a reformer typically contains paratTins, napLthenes, and aromatics
(no olefins) containing five to 11 carbon atoms. This generally limits the naphthene and
aromatic content to one-ring structures. For this range of components it is possible to
detennine all of the components with gas/ liquid chromatography. A complete
---------------------.
10 163

;Ml,down of refo.rming naphtha can be represented by about 50 major components.


this still results in a large number of possible reactions. it is feasible to develop a
Jtll"'''''' model which represents the m'\ior reactions in a reformer. Such a model has been
. developed and published by Henningsen. et.a1 .... Turpin6' has also published a guideline
(or constructing a predictive. component based model for naphtha reformers .

. Table 10.4
Typical Reactions in Reformer Reactors:

lfydrocracking (Cracking plus Hydrogenation) Reactions:

Po+H2 e:> Pm + Pom


Nn + H2 e:> Nm + Po-m (side chain removal)
(2N)n + H2 e:> (2N)m + Pn-m (side chain removal
An+H2 e:> Am + Pn-m (side chain removal)
(2A)n + H2 e:> (2A)m + Po-m (side chain removal)
(2N)n + H2 ~Nn (ring opening)

Hydrogenation Reactions:
On + H2 e:> Pn

Dehydrogenation Reactions:
Pn e:> Nn + H2 (cyclization)
Nn ~ An +3H2
(2N)n e:> (2A)n + 5H2

Isomerizalion:
n-Po <:0:> i-Po
MCP <:0:> cyclohexanc
DiMCP <:0:> metbylcyclohexane

Coking:
An +( 2A)m <:0:> (4A}n+m + 3H2 . (condensation)
2(A)n <:0:> (3A)2n + 3H2 (condensation)
(3A) and (4A) <:0:> Coke + H2

Reactions:
Platinum on a silica base is commonly used for reforming catalyst. It is deactivated by
hydrogen sulfide, sulfur compounds, nitrogen, and oxygen. Therefore, the feed to a
naphtha reformer is first hydrotreated in a "desulfurizing" reactor which has a chrome-
molybdenum catalyst. After hydro treating, the naphtha is stripped with reformer
hydrogen to remove hydrogen sulfide.

Kugelman 66 has studied the reaction equilibrium for C6 through C9 hydrocarbons and
found that all types of reactions in the refonner are equilibrium limited except the
hydrocracking reactions.
164 Refinery Reactor Systems
The dehydrogenation reactions take place very rapidly, followed by the isomerization
reactions which are also rapid. The cyclization reactions and hydrocracking reactions
take place much more slowly. This accounts for the decreasing temperature drops across
the reactors. Table 10.4 presents a list of some of the typical reactions which take place
in naphtha reformers.

Gary and llandwer'.'" report the following conversion data for low pressure. refooners
producing aromatics from a 155 to 345 degrees F (68.7 to 174.2 degrees C) TBP naphtha:

a) 98 % of the feed naphthenes are converted to aromatics:


,I: MCP and cyclohexane make benzene
i Dimethylcyclopentane and cycloheptane form toluene
Dimethylcyclohexane and methylcyc10heptane produce xylenes
::
,Ii

b) Paraffins yield the following quantities of aromatics:


One mole ofP6 produces produces 0.05 moles of benzene
One mole of P7 yields O. 10 moles of toluene
One mole oiPS prori.uccs 0.25 moles of xylene
Onc mole Of P9 give5 0.45 moles of A9
One mole of PlO yic:ds 0.45 moles of AIO

10.1.3.2
Isomerization
Figure 10.5

,Gas
Isomerization Process
Hydrogen

Stabilizer

Separator
C5/C6 Feed
10 165

~ er:allnformation:
isomerization process is used to rearrange straight ch!lin molecules into branched
The primary uses of this process in oil refineries are to convert n-butane into
isol)utalne, and to convert the CS/ C6 normal paraffins in light gasoline (CS to 180
. degrees F [82.6 degrees C]) into the corresponding isoparaffins. There are many
variations of this process, but the flow sheets are all similar.

Figure 10.5 shows a typical process that converts C5/ C6 paraffins into the corresponding
isoparaffin isomers. The l'nit may be "once through" or may se;>arate and recycle normal
paraffins back to the reactor to increase overall conversion. The recycle process option is
shown in dashed lines.

Several schemes are used to separate normal paraffins for recycle. The isomerate may be
processed in a molecular sieve that selectivdy removes the normal paraffins, or a series
of distillation columns may be used. One distillation arrangement is to send the
stabilized isomerate to a C5/ C6 splitter and then send the C5 overhead to a C5 splitter
where the isopentane is removed. The fresh charge to the unit is also charged to the C5
splitter, and the splitter bottoms is the feed to the isomerization reactor(s). While recycle
increases conversion, it also adds substantially to the equipment cost and may not be
economically justified for a given refinery.

The F-I octane number of the light gasoline mixture is typically increased by 10 to 12
numbers for the once through process and by about 20 numbers for the recycle process.
A comparison of the octanes for C5 and C6 paraffins is given in Table 105
I

Table 10.5
I
F-I Octanes for C5 and C6 Paraffins" \

Paraffin F-I Octane


n-pentane 61.9 J
Iso-pentane 92.3

n-hexane
!I
24.8 I
2-2 dimethyl butane 91.8 I'
2-3 dimethyl butane 101.7
2 methyl pentane 73.4
3 methyl pentane 74.5

Operating Conditions:
Isomerization is favored by low temperatures and is somewhat independent of pressure.
Typical temperatures for isomerization reactors are in the range 300 to 450 degrees F
149 to 233 degrees C). Pressures are commonly in the range 300 to 500 psig (21.7 to
""."J.J bars), but may be higher for some processes.

'I

.. ",.;
166 Refinery J(eaClUr "y.)I''''I~"
.-
A hydrogen blanket is used to minimize cokeJonnation on the catalyst. The mole
of hydrogen to hydrocarbon in the reactor is in the range of 1.0 to 3.0. Hvdroa ..n
consumption is small, although there is a smal1 amount of hydro cracking and benzene in
the feed will be converted to cyclohexane. Liquid yield of isomerate is 98.0 LV % plus.

The light naphtha feed to a CS! C6 isomerization unit is comprised of fifteen or fewer
actual components All of the components may be easily identified with gas! liquid
chromatography.

Reactions:
Mcst processes use a platinum catalyst with a small amount of organic chloride to
promote isomerization. Zeolite catalysts are also used. The reactor outlet closely
approaches equilibrium mixtures for the CS and C6 paraffins. If normal butane is
present in the feed, it will also be partially isomerized.

The equilibrium mixture of CS's will be 75 to 80 weight percent isopentane, depending


on the reactor temperature. The equilibrium mixture of C6's will be 86 to 90 weight
percent hcxane isomers. Equilibrium favors the conversion of normal hexane to 2 methyl
',cntane and 2-2 dimethyl butane, with much lesser quantities of 3 methyl pentane and !-
3 dimetl,yl but?ne being formed.

Benzene in tho feed is saL,'ated te cyclohexane in the hydrogen environment There is .


,I
also some hydrocracking of cyclopentane and methyicyclopcntane in the reactor. Table
10.6 gives some of the typical reactions in CS! C6 isomerization reactors.

Table 10.6
Typical Reactions in Isomerization Reactors:

f/ydrocracking:
Pn + H2 ~) Pm + Pn-m
Nn + H2 ?:> Pn

Jsomerizalion:
n-C-l
n-CS
"', i-C-l
.-CS
n-C6
""
?:> 2-2 DMB
n-C6 "', 2-MP
n-C6 2-3 DME
n-C6 "" 3-;'U'
?:>
fiydnJgenoflon:
A6 +3H2 ",. CH

There is a mild heat release from the isomerization reactions. Therefore, it may
desirable to cool the reactor eflluent between multiple reactor beds. Saturation
hydrocracking rea.:t:ons also account for some of the heat release in the reactors.
10 167

lation and Polymerization


Alkylation and polymerization share a common purpose of converting light olefins into
motor gasoline. The primary olefins for these processes are propylene and butylene, but
some amylene also finds its way into the feed stocks. Polymerization was the earlier of
the processes to be used commercially, and dates back to the 1930's. Alkylation also
dates back to the 1930's, but it did not come into general usage until the World War 11
years when it was used to manufacture high octane aviation gasoline.

The polymerization process has lower operating costs and much lower construction costs
than the alkylation process. However, the polymerization reactor produces about 0.8
barrels of gasoline for every barrel of olefin tQat reacts. On the other hand, the alkylation
reactor combines each barrel of olefin with ail average of 1.25 barrels of isobutane to
produce an average of 1.75 barrels of high octane gasoline blending stock.

Reformulated gasoline calls for reduction of olefin content. This makes polymer gasoline
(100 % olefins) an undesir"ble blending stock. Furthermore, while the polymer gasoline
has a research octane (F-I) of 96 to 98, the motor octane (F-2) is about 12 numbers
lower. The research octane for alkylation gasoline is from 92 to 94, and the motor octane
is only one or two numbers lower. Gasoline is now marketed by the average of the two
octane tests, i.e., "(R +M)/2". It is obvious that alkylation gasoline is more desirable than
polymerization gasoline when this specification is considered. Therefore, many refiners
with alkylation units have shut down their polymerization units.

10.1.4.1
Alkylation

Figure 10.6
Alkylation Process
Isobutane Recycle LPG Propane

nbutane
ISObulane Acid Product
--l-~
Reactor Settler Separation Alkylate
Olefins:
C3
C4-
CS Acid catalyst
I'

, ill
168 Refinery Reactor Systems

General Information:
. A block flow diagram for the alkylation process is shown in Figure 10_6. An olefin-rich
feed stream is combined with isobutane and reacted over an acidic catalyst to produce an
alkylated gasoline product (alkylate)_ A large recycle of isobutane is combined with the
fresh feed to the reactor to minimize formation of undesirable products that contaminate
the catalyst.

The product mixture is separated from ,;le acid catalyst, and the catalyst is C;[,_~cl1ated
back to the reactor. The product mi,,'!ure is separated, and a large stream high in
isobutane is recycled back to dilute the fresh feed stock_ Sufficient fresh isobutane feed
must be added to the process to meet the chemical consumption in the alkylation
reactions and the losses of isobutane from the system into the fractionated products, i_eo,
propane, normal butane, arid alkylate_

The most desirable olefin feed stocks are butylenes; however, refineries that do not
polymerize propylene or extract it for petrochemicals may also feed propylene to the
alkylation unit. Small quantities of amylenes (CS olefins) may also be present in feeds
p:epared hy stabilizing catalytic 0;- thermally cracked gasolines_ Amylene produces a
slightly i<wccr OC1F1C alkyl21c gasoline than butylene_
C i

There are two basic pro;:;esses in use today: hydrofluoric acid (!-IF) alkyl2tion, and
sulfuric acid (H2 SO.) alkylation. In general, the feed stocks are the same; however, the
operating conditions in the reactor are quite different_ Both processes form acid soluble
oils (ASO's) which dilute the acid_ These undesirable side-products must be removed
from the acid to restore the catalyst activity, HF units have regeneration facilities to
purify the acid; the acid from H 2 S0 4 plants is usually sent ofl:site for purification_ The
fraClionation portion of the process is similar for both types of units. A comp?rison of
the alkylate qualities for the HF and H 2S0 4 processes is ShOl'.'11 in Table i 07_

Table 10.7
Typical Octanes in Alkylation

Feed Olefin HF Units thSO~ Units


F-J Octane F-2 Octane F-l Octane F-2 Octane
propylene 91-93 89-91 89-92 88-90
bUlyienes 94-95 91-92 95-96 92-93
amylene 91-92 90 92-93 91

It is becoming more common to pretreat the feed to alkylation units to improve the
quality of the alkyl ate and to reduce the consumption of acid catalyst. Butadienes and
di-01cfins tend to produce ASO's in alkylation units, and can be converted to olefms in
hydro isomerization pretreatment units. For HF units, it is also desirable to convert
butene-I to butene-2 to increase the octane of the gasoline produced. Isobutylene is one
/0 169

. least favorable C4 olefin isomers for alkylation, and one pretreatment scheme is to
it with methanol in an MTBE plant to remove it from the feed to the alkylation unit.

: ()Ipt,ratiing Conditions:
alkylation reactions are highly exothermic and the reactor(s) must be cooled to
control the reactions and avoid formation of heavy polymer products. HF alkylation units
use cooling water to remove the heat of reaction, with the reactor acting as a heat
exchanger. Sulfuric acid units use either contact reactors with effluent refrigeration or
L'.: c;ucacle reactors with auto-refrigeration.

Typical operating temperatures for HF alkylation are in the range 60 to 120 degrees F
(15.9 to 49.2 deg C). Pressures are as needed to keep the system in the liquid phase and
range from 100 to 150 psig in the reactor (7.9 to IIA bars). Lower temperatures improve
alkylate quality.

For H2S0. alkylation, temperatures range from 25 to 55 degrees F (-3.6 io 13.1 degrees
C) with 35 to 40 degrees F (2.0 to 4.8 degrees C) being typical. Pressures are 10 psig
(1.69 bars) or lower for auto-refrigeration units in which isobutane refrigerant is flashed
off to cool the reactor. For effluent refrigeration systems, a back pressure from 50 to 70
. p.ig (4.5 to 5.8 bars) is held against the contactor to keep vaporization from occurring in
the contactor and acid settler.

Isobutane to olefin volume ratio is an important control variable for alkylation units.
This ratio varies between about 6.0 and 12.0 for commercial units. At lower ratios,
polymerization and formation of ASO's increases, as do "self-alkylation" reactions that
consume additional isobutane and form light saturated hydrocarbons. Increasing this
ratio results in an improved alkylate quality and a decrease in undesirable by-products.

The feed to an alkylation unit is easily analyzed and typically consists of about ten
hydrocarbon components. The alkylation reactions have been thoroughly researched and
it is possible to write a set of reactions to describe the process.

Reactions:
The following light olefins are commonly fed to alkylation reactors: propene, isobutene,
butene-I, cis-2-butene, trans-2-butene, and amylene. The major reactions are:
C3" + IC4 c::> C7 alkylate
C4- + IC4 c::> C8 alkylate
C5- + IC4 c::> C9 alkyl ate
Other reactions also occur and an alkylate gasoline is produced that consists of
isoparaffins from C5 through C 13. There are many isomers of C6, C7, and CS paraffins
producd by the reactions. Conversion of the olefins is complete, but the isomer
distribution of C8 compounds does not approach an equilibrium mixture.

alkylation units produce propane from hydrogen transfer to the propecie as follows:

C3- + IC4 c::> C3 + C4-

:' I
::. . 1I1
,I
I
r
,.
f
170 Refinery Reactor Systems

The C4 olefin that is produced reacts with another isobutane molecule to produce a CS
alkyl ate component. Note that this consumes twice as much isobutane as a "normal"
alkylation reaction. Data from Hofmann" indicate that H,SO. units also produce propane
when alkylating propylene. According to Albright', several refiners commented at a
1965 session of the National Petroleum Association that from 0 to 10% of propylene fed
to their H 2 SO. alky unit was converted to propane.

Amylene also undergoes a hydrogen transfer reaction to produce isopemane in both Hr


and H 2SO. reactors. Interestingly, all olefins produce some isopentane and some C8
alkylate indicating that many side reactions are occuning. Albright" presents a good
treatise on the' chemistry of alkylation.

Typical reaction products for alkylation are given in Table 10.S. Note that only the major
isomers have been listed in this table.
i
i
I" Table 10,8
Reaction Products from Alkylation of Olcfins with lsobutane

ReaCi 9J:J:ccd Reactor Product Car!i9" Number


I!'
0 propane 3
C3,IC., IC4., cis2-C4., tr2C4- isobulane
0, lC4., IC4., cis2-C4-,lr2-C4, cs isopcmanc 5
C3,IC4., 1C4, ci52-C4-, 0'2-<:4., CS- 23 dimcthylbutane 6
C3, IC4, IC4-, cis2-C4-, tr2-C4-, CS- 2-3 dimethyIpentane 7
C3, IC4., !-C4, Ci51-<:4., tr2-C4-, CS- 2-4 dimethylpentane 7
C3, IC4-, I-C4., cis2.(:4-, tr2-C4, CS- 224 lrimethylpentane 8
C3',IC4-, IC4, cis2.(:4-, tr2C4, CS 233 trimcthylpentanc 8
C3-, IC4., IC4-, cislC4-, tr2C4., CS 234 trimctl>ylpentanc 8
0, IC4. 1C4-, cis2-C4., tr2C4, CS- 2-3 dimclhylhexanc S
0, lC4., 1C4, c;s2.(:4., lr2C4., CS 2-4 di 11Iolhyl hexanc
,
. i' 0-,IC4, 1C4-, cis1-C4., tr2-<:4-, cs 22S trimethylhcxanc 9
0,IC4-, IC4-, cis2-C4-, tr2-C4-, CS Cl 0 paraflins 10
1 0-, IC4., 1C4-, cis2-C4., tr2-C4., CS C 1I paraffins II
0, IC4., 1C4, Ci52-C4., tr2C4., CS- C 12 paraffins 12
0-, IC4, l-C4-, cis2-C", tr2C4., CS C 13+ paraffins 13+

:VOle: /iF a/l..y/ation always produces propane; H2S04 a/l..y/ation production of propane depends on
operalirfg conditions.

Butene-l produces lower octane alkylate in HF reactors than butene-2; H2S04 reactors
produce equal quality alkylate from butene-I and butene-2, The alkylate from cis-2
butcne and tT ans-2 butene are equal in quality for both types of reactors. lsobutylene
I. produces lower quality alkylate than the butene-2 isomers for both types of reactors,
I..
,
I

; , Empirical methods:
t! Simple expressions may be used to correlate the alkylate yields and isobutane
I I
, t. consumption from the alkylation process. This allows the use of simple, predictive

~~ ---~- - -~--
10 171

1Il0<"'" for alkylation reactors in which an a1kylate composition is assumed and the yield
predicted from the feed composition.

The coefficients presented in Table 10.9 are minor modifications from the ideal
theoretical yields and requirements. They have proven useful in predicting yields for
both HF and H2S0 4 units. They may be tuned as needed to match a particular plant.

Table 10.9
Yield Factors for Alkylation

Qlefin bbls IC4 consumed! bbls A1kylate produced! bbls Propane'produced!


barrel olefin barrel olefin barrel propene-
propene 1.33 1.77 0.16
butenes 1.16 1.75
amylenes 1.00 1.65

- Normally for HF reactors only

There are several values reported in the literature for the heat of reaction for the various
olefins. Hengstebeck" reports the heat of reaction to be 630 to 700 BTU!lb of reacting
isobutane. Nelson" reports the heat of reaction to be: 350 BTUI Ib alkylate for propene,
315 BTUI Ib alkylate for butenes, and 250 BTU! Ib alkylate for amylene. Gary and
Handwerk74 report that the heat of reaction is in the range of 124,000 to 140,000 BTUI
bbl of isobutane reacting. Table 10. I 0 lists the above heats of reaction on a comparable
basis and includes values calculated by the author from assumed alkylation products.

Table 10.10
. Beat of Reaction for Alkylation

Basis: BTUI Ib olefin [kj I kg olefin]


~

Olefin Hen!1;stebeck' Nelson ~uthor-HF Author-H 2S04


propene 918 [2133] 833 [1935] 855 [1986] 832 [1933]
mixed c4's 636 [1477] 646 [1501]
mixed c5's 580 [1347] 468 [1087]
isobutene 517 [1201] 517 (1201]
butene-1 642 [1491] 642 (\491]
butene-2 606 [1408] 606 (1408]
I-pentene 599 [\391] 585 [1359]

For a mixture ofbutenes, Gary and Handwerk = 530 to 595 BTUllb


[1231 to \382 kjf kg]
..
.. .
Co mpuled al average of range given.
,-

172 Refinery Reactor Systems

10.1.4.2
Catalytic Polymerization

Figure 10.7
Catalytic Polymcriz2 l ioa Process

Tubular Reactors: Bed React:>rs:

Recycle
Olefin LPG Olefin _ _-'-----,- ~ LPG
Liquids Liquids
Rich Feed Rich Feed
Water Product Product
Quench 'Separation
Water +
Steam
Gasoline
Reactorls) Gasoline

General Information:
Block flow diagrams are shown for the catalytic polymerization (cat poly) process in
Figure 10.7. The process is very exothermic, and it is necessary to remove the heat of
reaction to prevent excessive polymerization. The two common now sheets are shown in
Figure 10.7: tubular reactors with water cooler jackets, and fixed bed reactors with cold
quench injection. Both processes are designed to control the lempera:u:'c in the rc"ctors.

This process requires much less capital expense than the alkylation process, and it was
once used instead of the alkylation process to produce gasoline from the light olefins
produced by the thermal and catalytic cracking processes. The need to reduce the olefin
content in gasoline and the superior quality of the gasoline produced by alkylation has
resulted in wide-spread disuse of this process versus alkylation. The cat poljC also yields
only about half of the gasoline volume per volume of olefin reacted versus alkylation.

Process Conditions:
The operating conditions for cat poly units are independent of the lype of cooling used in
the reactors. Typical ranges for temperatures and pressures in the reactors are:
Pressures from 500 to 900 psig (34 to 61 bars)
Inlet temperatures from 300 to 350 degrees F (\49 to 177 degrees C)
'I Bed outlet temperatures from 350 to 425 degrees F (177 to 220 degrees C)
Tube outlet temperatures < 400 degrees F (205 degrees C)

The reaction heat is also controlled by circulation of recycle to dilute the feed olefins
Both propylene and butylenes are commonly charged to the process. Feed stocks may
also contain small quantities of amylenes.

------~- ~-.-.
173

O'Oiv."""lion varies, depending on the operating conditions and the activity level of the
Conversion tends to be more complete for the iighter olefins. The following are
'tvJ)ic;al olefin conversions to c;at poly gasoline:

90 to 95 percent conversion
75 to 85 percent conversion
65 to 75 percent conversion

Reactions:
The most common catalyst is phosphoric acid. It is necessary to pretreat the feed to
remove sulfur and basic materials which neutralize the acid. It is common to caustic
wash the feed to remove mercaptan sulfur followed by water wash and drying,. A
controlled amount of water is injected into the process to ionize the acid c;atalyst and
promote the teactions. Excessive temperatures in the reactors deposit coke-like materials
on the catalyst.

The primary reactions which take place are dimerization reactions. According to
Thomas", propene polymerization yields about 90 percent dimer (olefin C6) and 10
. percent trim er (olefin C9). Butylene forms mostly dimer (olefin C8) and amylene forms
.,. mostly the dimer (olefin 10). Some measure of control on the olefin distribution of the
product can be maintained by adjustment of the operating conditions.

Volume shrinkage is apparent when the volumes of the reactants and products are
compared:
propylene + propylene = C6 olefin
0.5 volume 0.5 volume 0.78 volume
I!
3 propylenes = C9 olefin 1.1

1.0 volume 0.71 volume 1I


Ii
:i
butylene + butylene = C8 olefin
0.5 volume 0.5 volume 0.82 volume

Nelson'6 reports the following heat of reaction data for polymerization: 670 BTUI Ib
propylene (1556 kj! kg) and 450 BTU! Ib butylene (1047 kj/kg). The author has
estimated the heat of reaction for amylene at 350 BTUllb amylene (814 kjf kg). Table
10.11 lists some typical reactions for catalytic polymerization.

Table 10.11
Typical reactions in Polymerization

C3= + Cl= => C6=


3 (Cl=) => C9=
C4= + C4= => C8=
3 (CI=) => C12=
C5= + C5= => <;:10=
--
174 Refinery Reactor Systems

I 10.1.5
Thermal and Coking
The thermal and coking reaction processes use only heat to crack the hydrocarbons andl
or to form petroleum coke. The earliest cracking processes were the thermal cracking
uniTs These processes were used to produce gasoline from the heavier crude oil fractions
and relied on heat and pressure to crack the oiL In addition to ;;;asoline, light hydl ocarb: '1
gases and liquids, he'lting oil, and a heavy tar (thermal tar) were produced in these units.
Since the cracking usually took place in the furnaces, it was necessary to shut these
i processes down on a frequent basis and "de-coke" the furnaces.
i Thermal cracking as a means of gasoline production has been largely abandoned. The
two thermal processes still in common usage are visbreaking and coke production. In the
visbreaking process, a heavy oil is cracked sufficiently to reduce the viscosity andl or
pour point to a desired leveL Small quantities of hydrocarbon gas and light liquids,
gasoline, and gas oil are also created by the process. The quality of these by-products is
usually poor, and they must be treated to remove sui fur and nitrogen and to improve their
stability

The most common coking process is delayed coking. In delayed coking, the heavy oil
feed is heated in a furnace and introduced into a large diameter drum where it rises and
deposits petroleum coke on the walls of the drum as the cracking reactions continue to
take place. Cracking is more complete than in visbreaking, and substantial amounts of
light gases and liquids, gasoline, and coker gas oils are produced. The light products
must be treated to remove impurities and improve stability. The light and heavy gas oils
are often charged to a hydrocracker or FCC for .further cracking into light products.

10.1.5.1
Visbreaking
General Information:
Visbreaking i3 a form of thermal cracking, the oldest cracking process. [<\ visbreaking,
. the goal is not to produce gasoline, but rather to alter the properties of a residual stream.
such as vacuum residuum and produce a more salable product. There is also a reduction
in the quantity of the residuum as some is converted to lighter cracked products.

A typical visbreaker flow sheet is shown in Figure 10.8. The heavy oil feed is heated in a
furnace to the desired reaction temperature and introduced into a "soaking drum" where
the cracking reactions continue to occur. The outlet from the soaking drum is quenched
with cold gas oil to stop the cracking reactions prior to entering the fractionating column.
The fractionator separates the lighter cracked products from the heavy product (tar).

A common variation of the process uses a furnace coil as the "soaker" instead of an
actual soaking drum. This may be accomplished with one furnace which contains two
10 175

hysicaJ coils, one for heating and one for soaking (reaction) .. Alternately, two separate
fiJlllal::es may be used for the heating and soaking coils.

Figure 10.8
Visbreaker Process
Gas

Quench

~r---Steam
Soaking
Drum Heating Oil
Stripper
Heavy A
~---;:r'v1-'---' Combination ~-------Tar
Column
Furnace

The cracking reactions are strictly affected by the parameters of time and temperature.
The soaking drum process provides more residence time for cracking than the furnace
cracking process, and therefore may be operated at a lower temperature to achieve the
same degree of cracking (conversion). Akbar and Geelen" have published a relationship
between cracking time and temperature for the same conversion level. This relationship
is shown in Table 10.12.

Table 10.12
Relationship of Time and Temperature in Visbreaking at Equal Conversion

Time, minutes Temperature. deg F Temperature. deg C


I 905 485
2 878 470
4 850 455
8 825 440
I

11
Each form of the process has advantages. The soaking drum process uses substantially I
less fuel than the cracking furnace process, Because the furnace operates at a lower i
temperature, run times before decoking are longer than the cracking furnace process. On
the other hand, the cracking furnace process is much easier to decoke and presents fewer
eil.;ronmental concerns. Decoking a furnace is relatively simple; decoking a soaking

L
-
176 Refinery Reactor Systems
drum requires the use of large quantities of high pressure ~ater which was must then be
processed to Temove contaminants.

Operating Conditions:
Operating conditions are dependent on the composition of the feed stOck and the design
objective for the unit. A limiting condition is reached for any resid at which the cracked
tar c"'; no lon:;::r hold th" a,phaltenes in solution and the tar becomes unacceptable as a
fuel oil.

Typical operating conditions are different for the soaking drum process and furnace
cracking process because of the time! temperature relationship of thermal cracking.
'. Temperature ranges are as follows:

Furnace cracking: 885 to 930 degrees F (475 to 500 degrees C)


Soaking drum: 800 to 830 degrees F (427 to 444 degrees Cl

Pressures vary over a wide range, depending on the design. Typical operations may vary
from 1SO psig to 500 psig (10 to 36 bars).

Yie'Js from the process also vary considerably. 'lhe crad:~:; produm are rich in
u"saturated hydrocarbons (olefins) produced by thermal crac;:ing. Table 10.13 presents
t)'pical yields and changes in the residuum accomplished 'xiln visbreaking.

Table 10,13
Typical Yields and Changes in Residue Properties

Prod~l Weight % ofChar"e


Butane and lighter 2-4
Pentane to 330 F (l65C) 5-7
Gas Oil up to 660 F (350 C) 10 - IS
Tar 75 - 85

Tar versus Feed: 15 to 35 degrees F (8.5 to 20 degrees C) pour poin(reduction


Viscosity reduction of25 to 75 %
Reduction in API gravity of 2.0 to Sf) "'Jmbers

Reactions:
The feed La a visbreaker contains a wide range of hydrocarbons of various classes and
boiling points The heaviest components in crude oil are usually present, with boiling
points approaching 1400 to 2000 degrees F (760 to 1094 degrees C). The heaviest
compounds consist of complex ring structures, both saurated and unsaturated. These
compounds may also have long paraffin-like side chains that cause the resid (0 have waxy
characteristics of high pour point and high viscosity.

-------_. ----- ..
177
I,
de_sired reactions in the visbreaking reactor are those that remove the long p8.raffin
chains and crack them into smaller molecules, thus reducing the viscosity and. pour
point of the resid feed_ Reactor conditions do not promote opening of ring structures;
however, some condensation of ring structures to higher molecular weight ring structures.
does occur. As in any thermal operation, some elemental carbon structures (coke) are
also formed. Because of the complexity of the feed and the reactions occurring, it is not
possible to develop stoichiometric reactions to represent the process. . Table 10. i 4
presents some of the typical reactions that occur in visbreaking.
I
Table 10.14
Typical Reactions in Visbreaking

Cracking Reactions:
Pn e:> Pm + On-m
On e:> Om + On-m
An e:> Am + On-m (side chains)
(2N)n e:> (2N)m + On-m (side chains)
(2A)n e:> (2A)m + On-m (side chains)

Condensation Reactions:
2 An e:> (3A)2n + 3 H2
An + (2A)m e:> (4A)n+m + 3 H2
An + (3A)m e:> (5A )n+m + 3 H2

Coking Reactions:
A ~ Coke +H2
2A ~ Coke + H2
3A ~ Coke+H2

The cracking reactions that take place in visbreaking are endothermic, and it is necessary
to supply this heat with a furnace. As the reactants are cooled with a cold gas oil quench,
the cracking reactions are suppressed.
178 Refinery Reactor Systems

10.1.5.2
Coking

Figure 10.9
Delayed Coker Pro!:ess

Quench
,-----,.-~-,/ Gas
o
L---:-'.L..-Gasoline
v

Stripper
<-I--Steam
L--_ _ _ Light Gas Oil

'---'---Heavy Gas Oil

_ 1 - - - - - Fresll Feed

0= valve open
ot fC~ Aj Main
Column
C = valve closed
Coke Drums furnace
I Rc = Hidden recycle
Steam

General Information:
This p:OCeSS reduces yields of residual material with severe thermal cra~king. The oil is
heated and allowed to destructively crack in a large vessel which provides liquid holdup
time iorthe heavy, unvaporized portion oflhe oil. Most of the reaction takes place ill the
liquid phase, with heavy polymers being formed and then being further dehydrogenated
to pe:roleum coke which deposits on the sides of the drum.

Figu:e 10.9 depicts a delayed coker process. The fresh charge is introduced into the
botto,,", of the main column where it mixes with the heavy liquid from the column wash
zone (the "hidden" recycle). Steam is injected into the main column bottoms and it is
heate-':: in a furnace. The velocity in the furnace is kept high so no cracking takes place
in the furnace.

The cot liquid! vapor mixture from the furnace is introduced into the bottom of the coke
drul71 where sufficient "delay" time is provided for destructive cracking. The reactions
take ?Iace in the heavy liquid phase in the lower part of the drum. The long residence
time 1~ the drum allows the heavy liquids to polymerize and dehydrogenate to petroleum
coke which adheres to the sides of the drum. The drum fills with coke from the bottom to
the top. The vapors that do not coke exit the drum and are quenched with cold gas oil to
stop the cracking process. The quenched vapors are fed to the wash zone of themain
Chapter 10 179

mn where they are cooled and the quencli zone liquid (recycle) is removed. The
'- ,portion of the main column above the quench zo.ne separates the cooled vapors into light
and heavy gas oils, gasoline, and gas.

The process is cyclic, and as one set of coke drums are filled they are taken off-line and
.another set of drums is brought on-line. The full drums are steamed, cooled, and the
bottom headers removed. High pressure, hydraulic drills are used to drill the coke from
the drums, with large pieces of coke falling through the open bottom headers into railroad
cars below. A considerable quantity of water ako exits with the coke and must be
recovered and cleaned up for re-use in the refinery.

Operating Conditions:
The charge to a delayed coker is typically a crude or vacuum column residuum stream.
The quality of the coke produced is dependent on the quality of the feed stock since the
sulfur and metals in the feed tend to concentrate in the coke. Generally, the coker feed
contains the heaviest materials in the crude oil, with boiling points approaching 1400 to
2000 degrees F (760 to 1094 degrees C).

Furnace outlet temperatures may exceed 900 degrees F (483 degrees C), with the coke
drum outlet temperatures in the range 780 to 830 degrees F (416 to 444 degrees C),
depending on the pressure. Coke drums are typically operated in the range 25 to 50 psig
(2.4 to 4.5 bars), but may be operated at higher pressures for some units. .

Process variables include the heater outlet temperature, the main column pressure, and
the temperature of the main column quenched vapors to the product fractionation zone.
The coke production is also directly related to the "free carbon" content of the feed as
measured by the Conradson carbon test.

Product yields vary, depending on the properties of the feed stock and the operating
conditions used in the operation. Table 10.15 gives some typical product yield ranges.

Table 10.15
Typical Yields from Delayed CI)king

froduct Yield, vol % offresh charge [weight.% of charge]


Wet gas 5 to 15
Gasoline 10 to 20
Total Gas Oil 40 to 60
Coke 30 to 50

I
11,
iI1-,
I

-~.--.---- I
11
;1
'1

\
180 Refinery Reactor Systems

Reactions:
The feed to a coker contains a wide range of hydrocarbons of various classes and boiling
point. The heaviest components in crude -oil are usually present, with lioiling points
approaching 1400 to 2000 degrees F (760 to 1094 degrees C). Sometimes the feed also
contains cracked residual materials from other processes in the refinery. Because of the
complexity of the feed composition and the large number of reactions that take place, it is
not ;;lssible to describe the coking reactor with stoichiometric equations.

Table 10.16
Typical Reactions in Delayed Cokers

Cracking Reactions:
Pn => Pm + On-m
On =>Om +On-m
Nn => Nm + On-m
cOn => COm + On-m
An => Am + On-m (side chains)
(2N)n => (2Nlm + On-m (side chains)
(2A)n => (2A)m + On-m (side chains)

(5N)n => <<;N)m + On-m (side chains)


(SA)n => (SA)m + Oil-m (side chains)

Deh_vdrogenation and CondensoliarJ &actions:

p C:>O +H2
0 <:o:>N
N <:0 CO+ H2
1;;1
CO <:0 A + 2H2
,'1."
N (~ (2N) ;. H2
A => 2A + 3H2
2N => 2A .;. SH2
2N => 3N +H2
2A => 3A +3H2

4N => SN + H2
4N => 4A + 9H2
4A => SA + 3H2

Coking Reactions:
2A <:0:> O:>ke ~ mlH2
3;\ <:0 Coke + m2H2
4;\ => Coke + m3H2
SA => Coke + m4H2

Interestingly, most of the cracking takes place in the liquid phase, with the coke drum
acting as a stirred-pot liquid reactor The furnace does not vaporize the heaviest portion
of the coker feed and it forms a liquid pool in the coke drum. The coking reactions are
endothermic and the. hot vapors from lhp. filffiace cool as they rise in the drum, with the
10 181

~,'ie!lt
components condensing and falling back into the liquid pool in the drum. The
liquids are polymerized and dehydrogenated to coke as they remain in the drum.

The level in the coke drum rises as the cycle proceeds, with a turbulent layer of polymer
tar on top of the coke deposit. It is necessary to monitor the level of the coke in the drum
and take the drum off-line before the level is such that tars are carried out of the coke
drum chamber into the overhead lines.

Three types of reactions occur in the coke drum: cracking, dehydrogenation, and coking.
In coking, these reactions are not reversible. Table 10.16 lists some of the typical
reactions that occur in coke drums.

10.1.6
Hydrogen Plants
General Information:
Refineries with large hydrocracking and hydrotreating operations require a supply of
hydrogen in addit;on to that produced in naphtha reforming. The most common way to
produce additional hydrogen is to steam reform natural gas.

Figure 10.10
Hydrogen Plant

Reforming High Temperature


Furnace Shift Reactor
Hydrogen
Natural
Gas -r-I~......,,_I Cooling
Hydrogen
Steam
Purification

A typical hydrogen plant is shown in Figure 10.10. Natural gas and steam are combined
and heated in a reforming furnace where the hydrocarbons in the natural gas are steam
cracked to an equilibrium mixture of methane, water. carbon monoxide, carbon dioxide,
and hydrogen. The hot mixture from the reforming furnace is cooled and sent to the high
temperature shift reactor where carbon monoxide is reacted with water to form carbon
dioxide and hydrogen

The effiuent from the high temperature shift reactor is cooled and fu.ther processed in a
low temperature shift reactor that combines additional carbon monoxide with water to
produce more carbon dioxide and hydrogen.

!, "" 'h n' .


182 Refinery Reactor Systems

The effluent from the low temperature shift reactor is de-watered, and the carbon dioxiqe.
- unreacted methane, and other impurities are removed to produce a high purity hydrogen
stream. Various processes are used for the hydrogen purification step.

Operating Conditions:
The natural gas is combined with a small amount of hydrogen from the process, heated to
70010 750 degrees F (371 to 399 degrees C), and charged to a desulfurizing reactor. It is
next combined with steam and preileated to 900 to 1000 degrees F (483 to 538 degrees C)
prior to entering the reforming reactor.

The steam reforming reaction is endothermic. and further heat is added such that the exit
gas from the reformer is 1450 to 1650 degrees F (788 to 899 degrees C). The pressure of
the feed to the reformer IS in the range 200 to 500 psig (\4.8 to 35.5 bars), with the
reforming reactions favored by low pressure and high temperature.

The mole ratio of steam to hydrocarbon feed is also a control variable and is maintained
in the typical range 3.0 to 6.0. Below this range, carbon formation can occur. As the

'I.:,
~" ratie is increased. the hydrogen product purity is increased.

,] The high temperatu; c shift reactor is operated in the temperature rant'-e 650 to 750
degrees F (344 to 399 degrees C) and the low temperature shift reactor is operated in the
range 400 to 450 degrees F (205 to 233 degrees C). New plant designs may not inciude a
low temperature shift reactoc since the incremental conversion in this reactor is small.

Traditional process designs use amine treating to remove the carbon dioxide in the
impure product from the shift reactor(s), followed by a methanation reactor to remove
an)' remaining carbon oxides from the hydrogen product. The rnethanation reactor is
operated at a temperature of 500 degrees F (260 degrees C). 2nd acts iike a reverse
reformer 10 convert carbon oxides back to methane.

Reactions:
The reforming reactor contains a nickel-based catalyst that is poisoned by suI fur l\
compounds; hence, the feed is desulfurized prior to this reactor. The reforming.Jeactions
are highly end athermic, and it is necessary to supply this heat by firing the furnace. The
~i base reaction occurring in the reformer is as follows:

Some carbon dioxide is also fanned in the reformer. Hydrocarbons heavier than methane
are also steam cracked to carbon oxides and hydrogen. with 100 percent conversion of
these compounds to methane and oxides of carbon. The mixture from the reformer is at
true equilibrium.

~.

i
II
10 183

shift reactors, the water gas shift reaction takes place to produce more hydrogen:

The water shift gas reaction is exothermic, and the heat of reaction is recovered by
preheating boiler feed water and generating steam. The products from the shift reactors
also approach equilibrium mixtures.

The methanation reactor promotes both the reforming reaction and the shift reaction.
However, the reactions proceed in the reverse direction and convert any remaining
carbon dioxide and carbon monoxide back to methane and water. The net reaction in the
methanation reactor is exothermic.

10.1.7
Ether Processes
Ethers have become the octane enhancers of choice with the phase-out of tetraethyl lead
from motor gasoline. These compounds also contain oxygen that is purported tdimprove
the combustion of motor fuel and reduce carbon monoxide in the exhaust gas.

Methyl tertiary butyl ether (MT6E) is currently the leading octane enhancer. It is
produced by reacting methanol with isobutylene. The e4 compounds produced by Fee
reactors have been the primary source for isobutylene, although there are also processes
that produce isobutylene by dehydrogenating isobutane.

The restriction on olefin content of reformulated gasolines has provided incentive for
refiners to also convert the C5 olefins in Fee gasoline to ether compounds. lsoamylenes
are reacted with methanol to produce tertiary amyl methyl ether (TAME).

10.1.7.1
MTBE Processes

Figure 10.ll
MTBE Process
C4 raffinate
C4 stream

I Methanol
Methanol~ Recovery
?-J MTBE
Column Methanol
Heater Reactor Reactor
' - - - - MTBE Product
184 Refinery Reactor
General Information:
A typical MTBE process flow diagram is shown in Figure 10.11. A stream cOl~ta:inillg'l
mixture of C4' s is combined with methanol and heated prior to entering the first re;;lCl()r.'
In the first reactor, about ninety percent of the isobutylene in the C4 feed is converted to '.
MTBE.

The e'Tluent from the first reactor is cooled and charged to a second reactor
approximately fifty percent of the remaining isobutylene is converted to MTBE. 1he
impure MTBE product is charged to the MTBE distillation column where the MTBE is .
removed as the bottom product. The unreacted methanol forms minimum boiling'
azeOlropes with the unreacted C4's, and distills into the MTBE column overhead.
mixture ofC4's and methanol is sent to the methanol recovery section of the plant.

In the methanol recovery section, the methanol is water extracted and sent to a methanoll ;. -.--~/ ~
. "()yI.
water separation column where the methanol is recovered. The raffinate from the
extraction column is a C4-rich stream. This stream is treated to remove traces
son!
oxygenates and then charged to an alkylation unit for reaction of the remaining C4
%)
.t ~
ole:ins.
I
A varia:inn of the process combines Ine reactor(s) with the MTBE column in a reactive j~("I '4
distillation column. This p~c>cess has the advantage of higher conversion rates, si;.-c~ the
wh'
equilibrium is driven toward MTBE production by the continuous removal of MTBE . ~
from the column reaction zone.
4
Operating Conditions: Me.
In petroleum refineries the primary source of C4 olefms is the FCC process. This process
produces a mixture of C4 olefins that includes isobutylene. lsobutylene is the least
desirable C4 olefin for the alkylation process. and its removal prior to the alkylation unit
to produce a valuable octane enhancer provides a double benetil to the refinery. It may
also be necessary to isomerize normal butane and dehydrogenate it to isobutylcne 10,
provide additional feed stock for MTBE production.

The preferred temperature range for the reactors is 100 to 200 degrees F (38 to 94 degrees
C). This is a compromise between low temperatures that favor equilibrium ~onversion to
l'>fTBE, and high temperatures that favor the reaction kinetics. By keeping the
temperatures reasonably low, the side reaction of methanol breakdown to dimethylether
is also minimized.

The pressure of the plant must be sufficiently high to produce the methanoll C4
ucotropes in the MTBE column. These C4 azeotrope, are approximately six mole
percent methanol at seven atmospheres and twelve mole percent at 17 atmospheres.

The methanol to isobutylenc mole rativ to the reactors is kept in the range 1.05 to 1.20.
Conversion of isobutylene foe a one reactor system is about 90 percent; for a two reactor
system the conversion is 95 Iv 97 percent. The reactive distillation process achieves 99
plus conversion levels.
10 185

catalyst used in MTBE reactors is an ion. exchange resin catalyst. Its' life is
.. prolonged by keeping the temperatures low, and the reactor temperatures are controlled
accordingly.. .

Equilibrium conversions of isobutylene to MTBE are generally achieved in external


reactor systems. Reactive distillation systems drive the conversion nearly to completion
by removing product MTBE from the reaction zone.

The main reaction is as follows:

Over 99 percent of the converted isobutylene forms MTBE. However, there are also
some side reactions that occur in the reactor. A small quantity of isobutylene 0.03 wt
%) is dimerized to diisobutylene as follows:

2(IC4-) c;> DIB (diisobutylene)

Isobutylene also reacts with any water in the system to form tertiary butyl alcohol (TBA)
which exits with the MTBE product:

Methanol reacts with itself to form dimethyl ether:

2(CH3 0H) c;> H 2 0 + DME (dimethyl ether)

While the side reactions are small, they must nevertheless be considered when modeling
these plants.

The heat of reaction when producing MTBE from methanol and isobutylene 15
approximately 250 BTU/lb ofMTBE produced. ,

:I
I
-
186 ]refinery Reactor Systems

10.1.7.2
TAME Processes

. Figure 10.12
Typical TAME Process

Heater
Reactor Raffinate
Methanol

Light Methanol
Recovery
Fee Fee
Gasoline TAME
Column Methanol
Heavy Reactor
FCC '-----TAME Product
i,l;

I Gen:,.d Information:
A T.AJv1E process flow diagram is shown in Figure 10.i2. FCC gasoline is split into light
and heavy fractions. The light FCC gasoline which is rich in CS olefins is fed to a
TAME reactor where it is reacted with methanol. In the first reactor, about seventy
I! percent of the reactive amylenes in the feed are converted to TAME.

The effiuent from the first reactor is cooled and charged to a second reactor where
approximately two thirds of the remaining r~"active amylenes are converkd to TAME.
The impure TAME product is charged to the T.\ME distillation column where the TAME
is removed as the bottom product. The unreacted methanol forms minimum boiling
azeotropes with light hydrocarl>ons in the light FCC gasoline, and distills into the column
overhead. The mixture of C4's, CS's, and methanol is sent to the methanol recovery
section of the plant.
-
In the methanol recovery section, the methanol is water extracted and sent to a methanoV
water separation column where the methanol is recovered. The raffinate from the
extraction column is a C4/ CS rich stream that is blended to gasoline.

A variation of the process combines the reactor(s) with. the TAME column in a reactive
Jistillation column. This process has the advantage of higher conversion rates, since the
equilibrium is driven toward T Al"lE production by the continuous removal of TAME
from the column reaction zone.

Operating Conditions:
In petroleum refineries the primary source of CS olefins is the FCC process. This process
produces a mixture of CS olefins. The isomers 2-methyl-butene-l and 2-methyl-butene-2
react \vith methanol to produce T.A.ME. Thc- isomer 3-methyl-butene-1 is inert and does
10 187

react. Some'refiners hydroisomerize the light FCC gasoline to oonvert the 3-methyl-
iUte:ne-1 to the reactive isomers 2-methyl-butene-1 and 2-methylbutene-2. This increases
the production of TAME and further lowers the olefin content of the blended gasoline
from the refinery.

The preferred temperature range for the reactors is 120 to 200 degrees F (49 to 94 degrees
C). The overall conversion from a two reactor system is about 90 % versus 95 % for an
MTBE unit because the reaction kinetics are slower for TAME formation than for
MTBE. By keepin3 the temperatures low, the sirie reaction of methanol breakdown to
dimethyl ether is also minimized. The molar ratio of methanol to reactive isoamylene is
kept in the range 1.0 to 1.5.

TAME distillation columns are operated at pressures comparable to MTBE columns.


Similar to MTBE columns, the unreacted methanol will form minimum boiling
azeotropes and exit in the column overhead: It is not necessary to make a clean
separation between the TAME and unreacted CS's since they will both be blended to
gasoline. Any C6's in the light FCC gasoline will also exit with the TAME product.

Reactions:
The catalyst used in TAME reactors is an ion exchange resin catalyst. Its life is
lt prolonged by keeping the temperatures low, and the reactor temperatures are contrail cd
a accordingly.
:y
Equilibrium conversions of the reactive amylene isomers to TAME are generally
achieved in external reactor systems. Reactive distillation systems drive the conversion
nearly to completion by removing product TAME from the reaction zone.

The main reactions are as follows:

2-methyl-butene-1 + CHJOH <:::> TAME


2-methyl-butene-2 + CHJOH <:::> TAME

The 2-methyl-butene-2 isomer is about 10 times as reactive as the 2-methyl-butene-1


JII isomer. The 3-methyl-butene-1 isomer does not react at all.
he
Any water in the system can react with isoamylenes to produce 2-methyl-2-butanol which
exits with the TAME product:

isoamylene + H 20 <:::> 2-methyl-2-butanol

Methanol can also react with itself to form dimethyl ether:

2(CHJOH) <:::> H 2 0 + DME (dimethyl ether)


r1
'I
'I
~" ,I
ill
I'
188 Refinery Reactor

iJ
~ ,
The heat of reaction when producing TAME from methanol and 2-methyl-butene-l
11' approximately 166 BTU/lb of TAME produced. For 2-methyl-butene-2 the heat
If i
reaction is 197 btullb of TAME produced.
11

10.2
Reactor Processes: Simulation Techniques
The first sec,ion of this chapter presents overviews for the various refinery reaction
systems. In this section, techniques are discussed that may be used to moud the,
reactor(s) in these processes,

Several techniques may be used to model refinery reactors with commercial simulators: :
black box, modified black box, empirical predictive, free energy minimization"
equilibrium, and stoichiometric conversion. The technique that is chosen is dependent on "
I:
the complexity of the reactions, the information that is available for the reactions, and
I)'
information that is available for the specific process being mode led, Table 10,17 lists
"'j tecl"'liques most likely to apply to the refinery reactors discussed in this chapter. Further
discu :on of ,11(; reactor models is give" in the sections below.

Table 10.17
Applicable Reactor Techniques for Refine~ Reaction Processes

Reaction Process bJwlicable Reactor Techniques

Catalytic Cracking Black box


H ydrocracking Black. box, Modified bh,ck box
il Hydrotreating Black box, Modified black box
I1
Catalytic Reformi ng Black box
Isomerization Equilibrium, Stoichiometric conversion
Alkylation Empirical predictive, Stoichiometric conversion
Catalytic Polymerization Empirical predictive, Stoichiometric conversion
Visbreaking Black box ~
Coking Black box
Hydrogen Plants Free energy minimization, Equilibrium
MTBE. TAME processes Stoichiometric conversion

10.2.1
Black Box Reactor Model
The black box model simply forces a mass balance betwe~n the feed to the reactor and,
the products from the reactoL There are no adjustments made to the composition of
reactor products from those supplied to the simulation modeL The rate of the
ij,' 1I

iW
----- ----~
""",'"r J0 189

~uellt composition as defined by summing the reactor products is adjusted as needed to


a mass balance with the fresh feed to the reactor. The reactor outlet temperature
and pressure are defined for the reactor effiuent.

Example 10.1 illustrates application of the black box technique to a coking process.

Example 10.1
Black Box Reactor: Coker Process

Plantin[ormation :
A set of data have been collected for a COker process as follows:

Feeds: bbllday API Iblbbl Ibfhour


Vacuum Resid 18,000 12.6 343.4 257,550
Purchased Tar 5,000 5.5 361.3 75,271
-------- ---------
Total Feed 23,000 332,821

Products:
Gas (C4 &. Ltr) 30,150
Gasoline 4,250 55.7 262.9 46,500
Light Gas Oil 8,000 29.6 307.2 102,400
Heavy Gas Oil 6,000 15.5 336.7 84,175
Coke 67,000
---------
Total Products 18,250 330,225

Laboratory assay data are also available for the feed and product streams. Operating
conditions are available for the unit operations in the coker process.

Problem Statement.
Develop a black box simulation model for the coker reactor (the furnace and coke drum):

SO/Ulioll :
I) Enter each feed and product into the simulator using the flow and assay data that are
available. The coke may be entered as a process "stream" comprised of a very heavy
hydrocarbon.

2) Determine the "net" reactor product and composition by combining all of the products:

Net effiuent = Gas + Gasoline + Light Gas Oil + Heavy Gas Oil + Coke
3) Determine the mass balance factor by dividing the mass of the fresh feed by the mass
of the net effiuent.
-
190 Refinery Reactor Systems
4) Multiply the net effluent by the mass balance _factor to generate an adjusted net
effiuent stream for the reactor. Note that in the simulator, the mass balance factor is
applied to all component flows in the net effluent.

5) Add the recycle stream to the adjusted net effluent and subtract the coke. The resultant
stream is the coke drum outlet, and its temperature and pressure are defined as the
measu,eo values frcm the plant. Nole :hat the recyrll! stream is excludedfrom the mass
balancing procedure.

This procedure is illustrated Figure 10.13 below:

Figure 10_13
Black Box Reactor: Coker Process

Define Temperature
and Pressure 6-,
,,

J"~
Gas ,,
Gasoline
L'GiJt Gas Ol I Mixing
Net Effluent _I
! Mass
Adjusted
Net Effluent I Strear;", Add
,,
Hi. / Gas 0; !
Coke
8:ock
I Balanoe
Blod
"i and s;;:_':~act
Coke
Drum OUt
Vacuum Resid Stream Total Feed _ i
Mixing
Purchased Tar Blod
Recycle '---_Coke

Sote that Jor this model, the ratio afthe individual reactor products is not changed from the original data
sJpplied to the simulator. Any mass imbalance petween the net ejJ1uent and rhe total fcd is applied evenly
la every product la generate the ccu"usted nel ejJluent.

This reactor is general, if! that the feed rates may be adjusted as desired and the caj-u.sled 1"1;:'[ ejJluent wili
always correspond to She new /otal mass of feed. However, the model will not adjust the ratios of the
individual products when the fatios of the feeds afe changed. For the above example. (he ratio of the ctJia,
to the net effluent would increase in the actual plant when the percent of purchased tar ;s increased. This
effect would not be predicted by the black box reactor above since the ratio of the products supplied to the
simulator is held constant.

10.2.2
Modified Black Box Reactor
The modified black box reactor is similar to the black box reactor. Bmh types of reactor
force a mass balance between the fresh feed and the net products from the reactor. The
modified black box reactor differs from the black box reactor in that at least part of the
net product is calculated by the reactor.

For example, a hydrocracker reactor is rnodeled as a modified black box. The apparent
products from a hydrocracker include the liquid products from the fractionation section,
the vapor products from fractionation, the cold low pressure separator gas, and the purge
':haJ~ter 10 191

However, the 'recycle-purge gas is treated in the process to remove sulfur and
... nitrogen compounds. In addition, there is a chemical consumption of hydrogen from the
hydrocracking reactions that must be accounted for in the mass and hydrogen balances
for the unit. Therefore, a modified black box reactor is used in which adjustments are
made to the reactor effluent to account for these effects.

Example 10.2 is an example of the use of a modified black box reactor to model a
hydrotreating process.

Example 10.2
Modified Black Box Reactor: Hydrotreater Process

Elant Information:

A kerosene product is hydrotreated to remove suI fur and to reduce the aromatic content
for improvement of the smoke point. The hydrotreating conditions are mild, and the
hydrogen consumption for the process is typically 125 SCF/ bbl of feed. The sulfur
content of the untreated kerosene is 0.05 weight percent. Ninety percent of the sulfur is
removed in the treating process. The recycle-purge gas is treated in an amine unit to
remove H 2S.

feeds: bbl/day API Ib/bbl Ib/hour


Sour Kerosene 12,000 41.5 286.0 143,000
MakeupH2 (2.28] 2,250

Total Feed 12,000 145,250


[ ] =MMSCFD

Products:
Purge Gas ( 1.80] 2.280
Stabilizer Gas ( 030] 835
Stabilizer Liquid 525 67.1 249.1 5,449 ~
Treated Kerosene 11,700 43.1 283.4 138,158

Total Products 12,225 146,722

Laboratorv assay data are also available for the feed and product streams. Operating
conditions are available for the unit operations in the hydrotreater process.

Problem Statement:
Develop a modified black box simulation model for the hydrotreater reactor. It may be
assumed that the hydrogen that is consumed leaves the process in the liquid products and
in the H 2 S that is removed in the amine treating of the recycle-purge gas.
'"

192 Refinery Reactor


Solution:
I) Enter these streams into the simulator: sour kerosene, treated kerosene,
liquid, makeup hydrogen, and recycle hydrogen (same composition as purge gas).

2) Enter a pure hydrogen stream that is equal to the hydrogen consumed by the process =
(125 SCFfbbl * 12,000 bbll day) I (24 hr/day * 380 SCFllb mol) = 164.471b mols! hr =
331.6 lbl \,e H2 censumed.

3) Detennine the H 2S production in the reactor: 0.000S*143,000 lblhr* 0.9 = 64.3Slbl hr


sulfur removed = 2.01 mols! hr H 2S produced = 68.5 Ibl hr H2S produced.

4) Mass balance the liquid products plus H2S against the kerosene feed plus hydrogen
consumed. Mass balance factor = (sour kerosene + H2 consumed) I ( H2S + stabilizer
liquid + treated kerosene) = (143,000 + 331.6)1 (68.5 + 5,449 + 138,515) = 0.9951.

5) Multiply the stabilizer liquid and treated kerosene streams by the mass balance factor
to detennine the adjusted flows for these products.

6: Create t',~ net rt'::Clor ejj7l1ent by r.dding the makeup H 2 , H2 S production, adjusted
sc2'::iizer li~:id, adj:.oled tre~~ed kerosccc, and subtract;:lg the hydrogen cmlsumed.

7) Add the recycle hydrogen to the net reactor el11uem and set the outlet ((\flditions to
complete calculation of the total reactor ei11uent. The modified black box procedure is
illustrated in Figure 10.14.

Figure 10.14
Modified Black Box Procedure: Hydrotrcater Process
Define Temperature and Pressure :,.,
,,
Makeup H2 ,,
Stabilizer
Recycle H2 ,,
Liquid Stream Liquid ,,
Mixing
,,
Treated
Block
I _p_rO_d_u_cts_.r_ _ _j Adjusted ,,
kerosene t- Liquid ,,
f-P_ro_dS_--.-; Stream ,,
Mass ,,
Balance Add and ,
.. Sour
H2
Cons
Block Subtract
Total Reactor
f Effluent
Calculation
il) Kerosene
,hj: '.
1'1 :
Block
L-_---.:-'it-;i2SI-~---J
H2S
14, Prod.
1'1 :
,rI
H2
VVt e;. &:..'i fu r
Cons.
H2 cOns:.Jmed, SCF I bbl
193

Predictive Reactor
The empirical predictive reactor model predicts the product based on the feed
composition and rate_ A typical composition is assumed for the product, and the rate of
the product"is predicted with standardized yield relationships_ Hence, as the feed rate and
composition change, the yield of the reactor product changes accordingly_

This model is very useful for predicting the amount of product that can be made from a
feed of given quantity and composition. To keep the model accurate, the assumed
composition for the product- must be updated when the feed composition to the plant
changes significantly_ .

The alkylation process is a good candidate for this type of reactor model. The quantity of
alkylate may be accurately predicted with yield factors for the C3, C4, and C5 olefins. A
typical alkylate composition is generated by supplying assay data to the simulator. As
long as the ratio of C3 and C4 olefins in the feed does not change greatly, the assumed
alkylate composition remains accurate and may be used. The isobutane consumption is
determined with a mass balance of the reacted oletins and the predicted alkyl ate
production. This type of reactor is illustrated in Example 10.3_

Example 10.3
Empirical Predictive Reactor: Alkylation Process

Plant Information:
An HF alkylation unit produces high octane alkylate gasoline by alkylating C3 and C4
olefins from by a catalytic cracking unit Plant data are as follows:

Feeds: bblldav API Ib/hour


Fresh charge: 8,050 65,969
0- 2,513 182.6 19,120
C3 896 177.6 6,630
rC 4 1,873 197.0 15,374
NC 4 586 204.0 4,981
C4- 2,091 214.5 19,036
IC, 91 218.5 828

Makeup IC 4 : 4,500 36,901


C3 124 177.6 918
IC 4 4,159 197_0 34,138
NC 4 217 204.0 1,845
------.-
12,550 102,870
,
194 Refinery Reactor Systems 4
Products:
Propane product
bb1lda~
1,387
API Ibfbbl
177.8
Iblhour
10,277
14
""-. ~

n-butane product 716 203.2 6,063 "d

Stabilized Alkylate 8,510 720 243.4 86,300 f


--------
Total Products 10,633 102,640 f
~
Chromatographic analyses are available for the feed, make-up ,sobutane, propane
product, recycie isobutane, butane product, and stabiliz.xl alkylate (C4 and C5 only). A
D86 distillation is also available for the stabilized alkylate product. The stabilized
C
alkyl ate contains 3:5 LV % NC .

j.
Standard yield factors for the unit are: f
Propane = 0.16 bbl! bbl C3-
C5 + alkylate = 1.78 bbl/ bb! C3- + 1.76 bbl/ bbl C4-

Proh{~!I'
Statement:
Develop an empirical predictive model for the alkylation reactor.

Solution:
I:I 1) Determine the true density of the C5+alkylate produced on :~e unit:

True C5+alkylatc = stabilized alkylate - (.:!'s -lCS in feed


True C5+alkylate = 8510 - 0.035*8510 - 91 = 8 J2 J k~ day
True C5+alkylate = 86,300 - 2,532 - S:8 = 82,94C :~.' hr
True C5+alkylate density = (82,940' 24) S12] = 245 : jb! bbl

Sore that wilh a simulator this entire step is accompl;she~ ~_. ., simply rerr.:Y.'/ng the nC4 and a portion ofthe
IC,[rom the supplied anylate slream to generate a true Cc' -all.ylate CO"?J5;:lOn.

2) Calculate the yields of C5+ alkylate and prop::e produce': :Tom the feed olefins:
Propane production = 0.16 * 2,5 J3 = 4: =Jb!/ day = 2.975 lb/ hr
C5+ alkyl ate from C3- = 1.78 * 2,5J3 = ~,473 bbl/ G~:.'
C5+ alkyl ate from C4- = 1.76 * 2,09J = :.680 bblf d;:-
Total C5+alkylate = 8153 bbllday
= 8153 bb!/day * 2':: : ib! bbl f :" = 83,263 lb! hr

In the simulator, a stream of pure propane is set of r-.! :a1culared pr: '::":::I]r; volume. The C5 +alkyJate
composillOn from step J) is ser at rhe calcu!aced C5+G:.-.~ ;!e voll.ln:~q

3) The le 4 consumption is determined by mass:alancing. tr;~ ,e<!ctor:


IC 4 = propane production + C5+alky!z=e production - ((3- + C4-)
lC 4 = 2,975 + 83,263 -(19,120 + 19,C:6) = 48,OS2 Ib/hr= 5857 bb!/ day
A stream ofpure IC, is se!- at the calculated mass cons:;:r.ption rate in :.;.;-! simulation model.

J
10 195

The net reactor effiuent is calculated by adding the fresh feed. makeup propane le..
C5.+alkylate production, and subtracting the feed olefins and the IC4
consumed by the reactions.

5) The total reactor effiuent is created by adding the recycle isobutane stream and the net
reactor effiuent. The temperature and pressure are set to reactor outlet conditions. The
whole procedure is illustrated in Figure 10.15.

Figure 10.15
Empirical Predictive Reactor: Alkylation Process
'. Define Temperature and Pressure

=J
NC4 & Native

,----<~ Isopentane
Recyde
Stabilized
Alkylate
---i" Component Isobutane

Separator Makeup
Block Isobutane


C5+Alkylate
Composition

Fresh
L_____r----1--"l1-_
C3 Prod.
_ _-'-....; Mass Stream Total
Reactor
IC4 Add and
Calculation C5+Alky Balance Effluent
Feed Reacted Subtract
Block 1-----,--->01 Block
Feed
' -_ _ _ _--' Olefins

Feed
Olefins
IC4
Reacted

The stabilized alkylate sample is used because a D-86. grm'ity. and LV % IC, and IC, are readily
available. Once the C5+a/J..yfate composition has been established iris not necessary 10 update this part of
the model unless the ratio oflhe feed olefins changes signijicanrlv.

The calculation block sets the rate of a pure propane stream Of the calculated production rate and the rate
of a stream with the C5+alJ...ylate composition at the calculated production rate. The mass balance block
sees the rale ofa pure isobulane stream at the mass rale necessary to balance the reactions.

I
...
J Refinery Reactor
196

10.2.4
Free Energy Minimization Reactor (Gibbs)
This is, the most general type of reactor. The free energy minimization
(commonly called Gibbs) determines the distribution of products for a reaction system at
thermodynamic equilibrium, Based on user defined species for the reaction mixture. the
technique locates the distribution of these species that give., the minimu;n free energy for
the system,

The method is applicable to problems in which the components (species) have


necessary free energy information available, Since free energy data are dependent
chemical structure. and petroleum pseudo-components do not have defined
structures, the method is limited to the real components in the simulator library for
refmery problems,

This method does not consider reaction rate, and the results represent thermodvl1an"ir.
equilibrium for an infinite time reaction. In the actual world, many reactions are 100
to ()ccur in the lioited residence time in a flow reactor. This lllay be represented
using the Gibbs method by ';lllitting the species that represent improbable reactions
or defining certain compounds as inen. For example, nitrogen may be defined as an
component and/or oxides of nitrogen may not be considered as possible species {or
given reaction system.

The method has the advantage of being completely general and predictive,
equilibrium constants are determined from the free energy data and the method
calculates the heat of reaction for the system, It is also not necessary to nrr'virl~
stoichiometric equations fOf lite possible reactions when using this method.

Candidates for the method in oil refineries include hydrogen plants. ammonia plants.
methanol plants. These processes are all related by the common use of steam r,,!'of1:ne1I5:
The method may also be used to represent the shift converters in the af()re:m(:ntionled.
plants by limiti'ng the species to those present for the shift reaction, :rhe Gibbs n1p,thrld
also finds utility in predicting the product mix and outlet temperature from
processes as sulfur incinerators. Example 10.4 illustrates the use of the Gibbs method
the steam reformer and shift converter in a hydrogen plant.
:
iF
-it
Example 10.4
'I;
I, ;
Free Energy Minimization Reactor: Hydrogen Plant Reformer
.\ '
~ :
Plant Information:
Natural gas is combined with a small slip-stream of hydrogen, heated to 750 degrees
desulfurized. The sui fur-free gas is mixed with steam, heated to 1000 degrees F.
charged to a reforming furnace coil to produce hydrogen, The product exits the reforrAI
10 197

1550 degrees F , is cooled to 770 degrees F, and charged to a shift converter. Plant
are as follows:

~oml1onent, mole % Natural Gas Steam H2 to Desulf


H2 O 100.0
H 2S 0.15 96.0
H2
N2 0.30
CO
CO2 0.45
CH. 92.69 4.0
C2H,; 4.75
C 3 Hs I.I3
I-C.HIO 0.15
N-C.HID 0.22
N-C5HI2 0.16

Total Flow, Ib mols! hr 3290.0 18,914.0 54.8


Temperature, deg F 100 950 lOO
Pressure, psig 400 450 500

Note that for the reformer and shift converter the products are predicted with the Gibbs
technique.

Problem Statement:
Develop a simulation model for the desulfurizer, reformer, and shift reactor.

Solution:
I) The hydrogen and natural gas are combined, heated to 750 degrees F, and charged to a
component separator block where the H2 S is removed.

2) The sui fur-free gas is mixed with the inlet steam, heated to 1000 degrees F, and
charged to a Gibbs reactor which represents the reformer. The only information provided
to the Gibbs reactor are the feed and the product outlet temperature of 1550 degrees F.
Based on the species available in the model component system, the Gibbs method
predicts the product distribution corresponding to an equilibrium temperature of 1550
degrees F. All hydrocarbons heavier than methane completely disappear in the reactor.
The resultant reactor effiuent contains H20, H2, N 2, CO, CO 2, and unconverted CH..
Note that the N2 is inert and does not react.

3) The effiuent from the reformer is cooled to 770 degrees F and charged to the shift
converter which is represented by a second Gibbs reactor. All species in this reactor are
marked as inert ercept H2, H20, CO, and C02. Thus, the only possible reaction is the
water shift-gas reaction: CO + H20 <:::> CO 2 + H2
n

198 Refinery Reactor


The shift converter determines the equilibrium yield of Hl from CO and calculates
resultant outlet temPerature based on the heat of reaction.

The simulation model is shown below in Figure 10.16.

I' :

I'
Fi!!ure 10.16
Gibbs Reactor 1\1 odds: Hydrogen Plant Reformer and Shift Converter

H2S tOoo F 770 F


H2 to
Desulf. ,----'------, Sweet Shi~
-~., Component Gas Refonner
f--.---.-y
Nar! Separator
Gas
Heater

Slezm
Cooler

,'~otes: Reiormer is Gibb"- leador with sp::.cifted outle..


tempf<!ture of 1550 degrees F. All reactions are pennttied.

Shift Converter is Gtbbs reactor with calculated outlet


tem:pe1'ilttft'. All species are inert except H2. -H2O, CO, C02.

10.2.5
Equilibrium Reactor

The equilibrium reactor is used to model specific reactions that reach thermodynamic
equilibrium. One or more reactions may be considered to simultaneously occur. As
previously illustrated in Example 10.4, the general Gibbs reactor technique- may be used
to model a single equilibrium reaction by limiting the species that react.

To use the equilibrium reactor technique, specific stoichiometric reactions must be


defined and the corresponding equilibrium constants supplied as functions of the reaction
temperature. Equilibrium constants may generally be provided in the form of an
Arrhenius equation. For some simulators, equilibrium constants may also be computed
using the free energy of formation data for the components in the library.

Example 10.5 illustrates use of the equilibrium reactor to model a butane isomerization
unit.
199

J!,~I"'t'.. ~ 10.5
Equilibrium Reactor: Butane Isomerization Reactor

Plant Information:
.. A mixture of butanes is fed to an isomerization reactor to convert normal butane to
isobutane. The product is used as makeup isobutane for an alkylation unit.

Feed: Mixed butane stream:


68 LV % NC., 31 LV % lC., I LV % lC5

Problem Statement:
Use an equilibrium reactor to model the isomerization reactor.

. Solution:
I) The mixed butane stream is supplied to a simulator. In the process, it is mixed with a
small amount of. hydrogen and heated to an ideal reaction temperature, where
isomerization is favored.

2) The preheated mixture is fed to an equilibrium reactor for which one stoichiometric
reaction has been defined:
NC. <:::> lC.
Note that none of the other components in the model will react. The mixture of NC. and
le. in the product will correspond to the equilibrium mixture. The reactor outlet
temperature is calculated from the heat of reaction.

3) The equilibrium constant for the butane isomerization reaction may be furnished in the
form of an Arrhenius equation:
In (le... ) = A + BIT
where: T = absolute temperature .

. Some simulators will supply the equilibrium constant (s) based on free-energy data in the
component data bank. The process is illustrated in Figure 10.17.

Figure 10.17
Equilibrium Reactor Model: Butane Isomerization Pmcess

Isomerization

C4 mixture Reactor

Heater

H2
200 Refinery Reactor Sysre~

10.2.6
Stoichiometric Conversion Reactor
The stoichiometric conversion reactor is useful when reactions are well defined, but the
corresponding rate and equilibrium data are not available or applicable_ in fact, the
reactions may not even approa::h equilibrium because of the space velocity in the reaclor,
etc_ and therefore it is convenient to specify the cO[iVersior, of the rClctants bas-::: on
actual operating data_

For this type of reactor, the stoichiometric equation is written for each reaction, and a
base reacting component is selected for each reaction_ The conversion p-crcentage of each
base component is specified by the model builder. Should the reactor be depleted of a
reacting component before al\ of a base component is reacted, the model builder has
options available such as stop reaction of the base component, supply the depleted
component as needed to react all of the base component, etc_ The options vary from
simulator to simulator for this situation_

For actllc I library compon'::nts, the heat of formation data for the components are used by
the sin: l!ator to nmpute the over:,1i heat oC reaction_ For user c'.;!tned cO":ponen's, it is
;>ccess:';-y to supply the appropriate thermodynamic prc;->erties lar the he\! of rec.,:tion
calculation_ Petroleum pseudo-components present a problem in this respect, since the
heat of formation is a function of both the component chemical class and the component
isomer structure_ Since neither of these characteristics is distinguishable for petroleum
pseudo-components, a generalized prediction of heat of formation is not sufficiently
accurate to predict a reliable overall heat of reaction, For conversion reactors based on
pe;roleum pseudo-components, it is best to compute ana apply the heat of reaclion
eXlernal to the reactor calculations,

I Example 10_6 illustrates use of a stoichiometric conversion reactor.

I Example 10.6
Stoichiometric Conversion Reactor: Catalytic Polymel'ization Reactor'

P fall! !nformation:
A mixture of C3 hydrocarbons is fed to a catalytic polymerization reactor, where the
p,opylene is reacted to produce gasoline, 90 % of the C3- produces C6- and 10 % ofllle
C3- produces C9-_ None of the other components react.

F ted. Mixed C3 stream


2 LV % C2, 40 LV % C3-, 55 % C3, 3 LV % IC4
I Flow = 4700 bbll day

Problem Statement:
Cse a stoichiometric conversion reactor iumodel the polymerization reactor.

"
II

,
I.
10 201

The mixed C3 stream is supplied to a simulator. In the process, it is mixed with a


, small amount of recycle (mostly propane) and heated to an ideal reaction temperature,
where polymerization is favored.

2) The preheated mixture is fed to a stoichiometric conversion reactor for which two
stoichiometric reactions have been defined:

Reaction: Base component Base comp. conversion %


2(C3-) ~ C6- C3- 90%
3(C3-) <::> C9- C3- 10%

Note that if the recycle stream contains significant quantities of the reacting base
components, it is necessary 10 reset the conversion percentages such that the quantities of
C6- and C9- produced in the reactions corresponds to conversion of the C3- in Ihe fresh
feed only. This is accomplished in a simulator with a calculation block and feedback
control/er,

3) The heat of reaction will be c.)mputed by the simulator. The model is depicted In
Figure 10.18 below.

Figure 10.18
Conversion Reactor: Cat Poly Reactor
1\ Feedback
~ Controller

, ,/ ..... ,
,, ,,
,, ''
Fresh " Reset ...-'.>.-_---,
,"" Conversions Calculation
Feed
,,/ Block

Reactions: Heater

L-._ _ _ _ Etnuent

Conversion
Reactor

Note: Initial conversion to C6- and C9- are set at 90 % and 10 %.


If the recycle contains C3-, the calculation block recomputes
the conversion level for the fresh feed only and the feedback
controller resets the reactor conversions.

I',
li
III
,[ r
202 Refinery Reactor Systems

References:

59 Silliman, JAm. Chem. Soc., 2, p 18 (1871-1872).

60 Sadeghbeigi, Reza, Fluid Catalytic Cracking Handbook, p 161, Gulf Publishing


Company (\995).

61 McCulloch, Donald C. and Roeder, R.A., "Find Hydrogen Partial Pressure"',


HydrocarbOl? Processing, p. 81-86, (February 1976).

62 Cooper, B. H., Stanislaus, A., and Hannerup, P. N., "Hydrotreating Catalysts for
Diesel Aromatics Saturation", Hydrocarbon Processing, p.83-87, (June 1993).

63 James H. Gary and Glenn E. Handwerk, Petroleum Refining Technology and


Economics, 3rd edition, Marcel Dekker, Inc., New York, (1994), p.I53.

64 Henningsen, J., Bundguard-Nielson, M., British Chemical Engr., Vol 15, p.I433-
1436, (1970).

65 Turpin, L.E., "Cut benzene out of Reformate", Hydrocarbon Processing, p. 81-92,


(June 1992)

66 Kugelman, A1an M., "What Affects Cat refortnel' Yield?", Hydrocarbon Processing,
p. 95-102, (Ianuary 1976).

67 James H. Gary and Glenn E. Handwerk, 'Pelroleum Refining Technology and


Economics, 3'd edition, Marcel Dekker, Inc, New York, (1994), p.206-207.

68 W. L. Nelson, Petroleum Refinery Engineering, 4tll edition, McGraw-Hill Book


Company, Inc., New York, (1958), p.212.

69 Hofmann, lE., "Ionic Reactions Occurring in Sulfuric Acid Part IJI", J. Org Chem.,
29, p. 1497, (1964).

70 A1bright, Lyle F., "Alkylation Process Using Sulfuric Acid as Catalyst". Chemical
Engineering, p. 143-150, (August IS, 1966).

71 Albright, Lyle F., "Alkylation: Chemical and Engineering factors for Reactor Design".
Chemical Engineering, p. 119-126, (July 4,1966).

72 Hengstebeck, R. J., Petroleum Processing, McGraw-Hill Book Company, Inc., New


York, (I959)

73 W. L. Nelson, Petroleum Refinery Engineering, 41h edition, McGraw-Hill Book


Company, [ne., New York, (1958), p.73?
10
203
H. Gary and Glenn E. Handwerk, Petroleum Refining Technology and
:cmrom'ics, 3n! edition, Marcel Dekker, Inc., New York, (1994), p.234.

Thomas, C. L., Catalytic Processes and Proven Processes, McGraw-HiII Book


'Company, Inc., New York, p.87-96, (1970).

76 W. L. Nelson, Petroleum Refinery Engineering, 4th edition, McGraw-HiII Book


. '. Company, Inc., New York, (1958), p.722.

77 Akbar, M., and Geelen, H., Hydrocarbon Processing, 60 (5), p. 81-82, (1981).
11.0
FCC (Fluid Catalytic Cracking) Processes
The catalytic cracking process is the heart of the modem refinery. This process is
major producer of high octane gasoline from the portion of the crude oil that is 1Ill':nelr'l
boiling than diesel fuel. In addition to gasoline, the process makes light heating oil, and'
iight olefins that may be converted to additional high-octane gasoline with the allcylallOII.;
process and! or may be used as feed slOcks for petrochemical operations.

The catalytic cracking process has been widely used since 1941. When introduced, it
a major improvement over the early cracking processes that were primarily thermal
nature. In catalytic cracking, the reactions take place on the surface of an ab~;orlberlt-l'YDe
catalyst which releases the light cracked products and retains the asphaltic, lar-ll~:e
products of cracking in the form of coke. The coke is subsequently removed from
catalyst in a regeneration step and the catalyst is returned to the process.

Early versions of the catalytic cracking process used mechanical devices to circulate
caTalyst between the reactor and the regenerator. As the process evolved, the catalyst'
circulation methods were improved. The second generation of catalytic crackers used air
!,)circulate the ca,alyst more rapidly, resulting in higher ..;onversions of the heavy gas
feed stocks to gasoline and lighter products than were achievable with the mech,.nir.JI1
systems. The Fee process represent~ the third generation of catalytic cracking, and
i,1
nearly completely superseded earlier forms of the process.
i
i 11.1
.i
FCC Processes: General Information
In the fluid catalytic cracking process, solid fluidization technology is used to bring
feed stock and catalyst into intimate contact. The catalyst is of a size and colnsi~>tel~CY'
that is easily fluidized in the reactor and regenerator vessels when aerated with a VaIlOr.
The fluidized catalyst is continuously circulated between the reactor and rC!!:en,era1tor:
vessels. The catalyst also serves as the medium to transfer heat from the hot re~:en,eralto(
to the oil feed entering the reactor.
I
I
In many Fee's, most of the reaction occurs as the hot, regenerated catalyst and oil feed'
travel through a standpipe (riser) into the reactor vessel. For these units the reactor serves
primarily as a disengaging pot for the spent catalyst and the oil products. Steam is also.
used to strip any remaining hydrocarbon products from the spent catalyst before it is
circulated to the regenerator for removal of the coke deposits by combustion in air.

The catalysts used in the Fee process have undergone major improvements over the
years. The results have been higher conversion levels, with a more favorable disHil)utlon:
of converted products, i.e., higher yields of gasoline and light olefins and lower yields
dry gas (ethane and lighter) and coke. Higher activity level catalysts have also aU()Wf:O

204
Ionr:.t"r 11

the cracking residence time to reduce the formation of undesirable by-

The Fee process has been modified to crack heavy oils to reduce the production of low
value residual products from the refinery. When cracking heavy oils, it is necessary to
use more than one stage of regeneration to remove the coke from the spent catalyst. The
higher regenerator temperatures for heavy oil cracking also require different metallurgy
in the regenerator.

FCC catalysts are subject to poisoning by metals, and modifications to the process and
catalyst have been made to reduce the effects of metals on the cracking products.
Because of the importance of this process, it is likely that it will be continuaIiy improved
in the future.

11.1.1
Process Description

Figure Il.l
Typical FCC Process

,-----------------------------------------------------~--~~------
: Lift Gas
light Gases
..
,,, Wet Cl's, C4's
, Gas r---1
Fee Gas Plant

r-------L __,.-__..-__-1
Gasoline
Stabilized
Gasoline

Reactor Effluent Main Rich Oil


Reactor
Gas Oil Fract. f---""":''''''':'--Le-a--'n Oil

Stripping Steam
Zone I----+- Light Cycle Oil

_Catalyst + Coke
---,.- .... Heavy Cycle Oil
,
,,,
Rue Gas ~

Regenerator
,,
,,
Air
Decant Oil ,:,
ReQ. Catalyst

A block diagram of a typical Fee process is depicted in Figure 11.1. Gas oil feed is
preheated by exchange with hot products from the main fractionator, mixed with hot,
regenerated catalyst, and charged to the reactor. Optionally, some unconverted "heavy
cycle oil" may be recycled to the reactor to increase conversion. The injection of a small
206 FCC Processes

amount of lift gas into the standpipe (riser) is also gaining popularity as a method to
reduce the poisoning effect of metals contained in the feed stock.

In the reactor, the products of cracking are separated from the spent catalyst. The catalyst
is stripped with steam to remove any remaining oil products and the hydrocarbon 1
product! steam mixture exits the reactor and proceeds to the main fractionator for initial
separation of the reaction products.
1

The coke-laden catalyst is circulated to the regenerator, where air is introduced to bum T
n. '.
the coke from the catalyst. Newer FCC designs burn the reaction coke to a mixture of
CO and CO2 , or completely to CO2 . The combustion reactions are exothermic, and a (:~
substantial amount of heat is transferred to the regenerated catalyst. This heat vaporizes
the liquid feed to the reactor and provides the overall endothermic heat of reaction for the
a'nl.
n.:
cracking reactions. f.!
-[he hot reactor effluent is cooled in the bottom of the main fractionator with a circulating 01
quench of slurry oil. The slurry oil product is a highly aromatic stream with a final
boiling point of apFoximately 1200 degrees F (649 degrees C). This heavy material is
It
generally sent to a coking unit or to another resid process. Optionally, a net product flow tt
of heavy cycle oil may be withdrawn from the main fractionator above the quench zone, c'
and some may be recycled back to the reactor to increase conversion.
i' 4!
1 ::<
The light cycle oil is withdrawn asa side product from the main fractionator and steam
stripped to remove light materials and improve the flash point. This product is suitable as
a blending stock for light heating oils. For use in low sulfur heating oils, light cycle oil
;1
1;'
requires hydrotreating to lower its sulfur content. 11.j

'.
-Cl.;~
The unstabilized gasoline and "wet" gas are overhead products from the main
fractionator. The gasoline is pumped to the FCC gas plant, where it serves as an
absorption medium prior to stripping and stabilization. The wet gas is compressed .and
sent to the FCC gas plant where it is typically cooled and processed in two stages of
:.
absorption to recover additional gasoline and C31 C4 hydrocarbons. Cl
There is a recycle loop between the main fractionator and the FCe gas plant. A lean oil
stream drawn from the main fractionator is sent to the second stage of absorption in the
4
gas plant to recover gasoline and e31 C4 hydrocarbons from the light gas product prior to
its use as fuel in the retinery furnac.es. The "rich" oil stream from the second stage of
absorption in the gas plant is returned to the main fractionator. In many designs a small
stream of light cycle oil is used for lean oil; however, it is also possible.t() draw a side
product of heavy naphtha near the top of the main fractionator for this purpose.

The gas plant stabilizer removes the C31 C4 hydrocarbons from the gasoline to produce a
suitable gasoline blending stock. Some FeC gas plants also have a splitter column to
separate the C3 and C4 hydrocarbons. The C4 oletins are nearly always sent to an
alkylation process where they are reacted with isobutane to produce high octane
isoparaffin gasoline. The e3 oletins may also be alkylated with isobutane; however; the

lL
11 207

yields are not as favorable as those for C4 olefins and they are sometimes used as
stocks to polymerization processes or petrochemical operations. .

1.1.2
Typical Operations and Control
.. The primary feeds to the FCC process are atmospheric and vacuum gas oil. Gas oil is the
native portion of the crude oil that boils in the approximate range 650 to 1075 degrees F
(344 to 580 degrees C). Depending on the crude oil, the gas oil contains impurities that
act as poisons and inhibitors to catalytic cracking catalyst. These include such metals as
nickel, iron, and vanadium, and basic nitrogen compounds. Some gas oils also contain
materials that lay down excessive carbon deposits on the catalyst and inhibit activity.
Historically, refiners have controlled these imp'urities with end-point control of the gas
oil, since they tend to concentrate in the higher boiling portions.

As the demand and market for residual products has decreased, refiners have increased
the feed to FCC processes to convert more of the crude oil to salable light products. Gas
oils produced on other units such as cokers are now being charged to FCC processes to
increase the overall gasoline yield from the refinery. This has resulted in the practice of
hydro processing these non-virgin gas oils to improve their quality as Fee feed stocks.
With the demand growing for Iow-sui fur heating oils, some refiners are now
hydrotreating all of the Fee feed stocks to remove sulfur prior to the cracking process.
Removing the suI fur, nitrogen, and other impurities from FeC feed stocks also has the
benefit of a more favorable cracked product distribution.

The cracking of heavy residue in catalytic cracking was pioneered by the TOTAL
company. In 1981 they introduced a two-stage regeneration process in which heavy
residue could be processed. Processing heavy residue in FCC's requires a second stage
of regeneration to bum the additional coke deposits versus FCe operations with
conventional gas oil feeds. This also results in higher regenerator temperatures and
requires special metallurgy in the regenerator internals versus the conventional processes.

Catalytic cracking is a low pressure operation, and most Fee reactors operate in the
pressure range 20~"p'sigG3.JQ_L1~Jm[s.absolute). The regenerator is maintained at
a slightly higher pressure. The main fractionatoi: operates at a small pressure differential
from the reactor cutlet.

Typical reactor temperatures range from 900 to 1025 degrees F (483 to 552 degrees C),
with regenerator temperatures up to 1275 degrees F (691 degrees e) for conventlonlfl
units and up to 1500 degrees F (816 degrees C) for units processing heavy residues.

The severity of a catalytic cracking operation is measured by conversion where:

Conversion, % = 100 * (v?lume fresh fee<i- .volume cycle stock) I volume fresh feed
=

208 FCe Pr(X:esse,

and cycle stock: ='Iight cycle oil + net heavy cycle oil + decant oil

Typical conversions range from 6S to 85 percent.

11.1.2.1
FCC Reactors
There are many different reactor designs in use today. Several oil companies, including
Shell, Exxon,. and TOTAL, have "developed their own designs, Three engineering
companies, UOP, Kellogg, and Stone and Webster, have designed and revamped many
units. Some designs use a side by side arrangement for the reactor and regenerator, while
other designs use downward flow from the reactor to the regenerator. All reactor designs
incorporate some type of catalyst disengaging mechanism such as cyclones.

It is beyond the scope of this book to discuss specific reactor! regenerator designs.
Moreover, it is not possible to model Fee reactors with mechanistic models when using
commercial simulators, and such discussion is not relevant to rhe techniques presented in
this book. Because of the complexity of the catalytic cracking reactions and the inability .
,
:!
I:
of pelroleum pseudo-co:i1ponenb L) represent chemical class, the Fee reactor is simply
represented as a black box when using commercial simulators. See Section 10. I. I for
,i
"

further discussion of the catalytic cracking reactions.


;i(
,
I, Note: It is possible to incorporate "modified black bor ~actors" into commercial simulator models in,"
Ili which spreadsheet calculations, etc., are used to predict a set of reactor products with defined properties;
i~
11 ~ed on supplied feed properties. Such models are usually based on proprietary information.
I]
!l
f~

11 .i
11.1.2.2
i'l
:j Main Fractionators
I]t
I, "

I1 Figure 11. 2 is a typical Fee main fractionator column. The hot reactor effiuent which'
I~ contains a substantial amount of steam is first desuperheated in the quench zone of the.
11

column. A pumparound circuit with the slurry oil (bottom product) is used for this'
n
H purpose. Heat is transferred from the slurry oil pumparound to the reactor fresh feed
.'
"
followed by one or more steam generators where the slurry oil is cooled by heating boiler
feed water to generate steam. The column quench zone does not contain fractionation
trays, but rather a series of "disks" and "donuts" to promote good contact for heat transfer
between the cold quench and the hot reactor effiuent.

The control point for the quench zone is the temperature of the slurry oil leaving the
column. To guard against cracking and coking in the bottom (boot) of the column, the
slurry exit temperature is controlled to be in the range 675 to 700 degrees F (358 to 371
degrees C). Many main fractionators have an injection of cold quench directly into the
boot as shown in Figure 11.2. For columns with this configuration, the slurry oil product
leaving the column is actually subcooled from saturated liquid conditions.

-----.~
------------------.........
11 209

Figure 11.2
Main Fractionator
H20 Coolers
Air Cooler
, -_ _ Wet Gas to
Gas Plant
HvyNaphtha Return 0--------.,
Heavy Naphtha <J---~ Sour Water
to product or lean oil

Heavy Naphtha
I

L ",,==r__ .-.:R.::e:::flu:::'~c-(+-J.._-f'f----<~ Unslabilized Gasoline


to Gas Plant

Pumparound

~------~:J Rich Oil Return

Main
Fractionator

L~ ..--.~ Light Cyde Oil


Steam
Slurry
Quench
r--r--<Oo!..-_ , Heavy Cycle Oil Pumparound
,
Steam Generators
- ,
Sub- _, ---~ Heavy Cycle Oil to product or recycle
Cool f4-----,
Boiler Feed H20

Slurry

Feed Reactor Ertluent

Decant OH ~S~e!!iHI~er}oC---.J

The next zone in the main fractionator is the heavy cycle oil zone. This zone consists of
a draw tray located a few trays above the quench zone, with a pumparound section for
further heat removal. Heavy cycle oil is a mixture of the lighter portion of the decant oil !i;

and the heavier portion of the light cycle oil and has a final boiling point of
approximately 875 to 925 degrees F (469 to 496 degrees C). When heavy cycle oil is not
withdrawn from the column for recycle to the reactor or charge to another refinery
process, these components distribute between the light cycle oil and the decant oil
products.

The main fractionator operates with a very delicate heat balance, and it is important that
the proper amount of heat be removed at the heavy cycle oil pumparound for a stable
operation. The stabilizer (debutanizer) reboiler in the FCe gas plant is often used for a
service in the heavy cycle oil cooling circuit. The temperatures in this reboiler and the
duty required are well suited to the use of heavy cycle oil as the heating medium. In
'. many Fee gas plants, heavy cycle oil heat is also used to reboil the stripper column. The
'; draw temperature for heavy cycle oil is in the range 575 to 625 degrees F (302 to 330
210 FCC PrO/.~:s;:.
-
degrees C) which makes heavy cycle oil ideal for use in steam generators. The heavy
cycle oil cooling circuit must always be carefully considered when a FCC process is
expanded. Should this duty not be expanded accordingly, the column will have severe
heat balance problems leading to unstable operation.

The light cycle oil draw tray is located a few trays above the heavy cycle oil pumparound
return tray. The light cycle oil has a typical ASTM D86 range of 390 to 700 degrees F
(199 to 371 degrees C) and is well suited for blending to heatir.g oil. This product is
steam stripped for flash point control. For many main fractionators, a small stream of
unstripped light cycle oil is drawn and pumped to the FCe gas plant for use as lean oil in
the secondary absorber. The rich oil from the secondary absorber is pressured back to
the main fractionator where the light ends are stripped into the overhead products. The
draw temperature for the light cycle oil is 475 to 500 degrees F (246 to 260 degrees C)
and a pumparound stream of light cycle oil is. sometimes used to reboil the Fee gas plant
stripper column.

, Many main fractionators have a top pump around of heavy naphtha that is used to reboil
!.'.:,'"
~'." :1 the Fer; gas plant stripper and also provide additional top reflux fOf the main column.
Fi'; Some desig,ls also Lse a small stream of the heavy naph'ha as lean oil for the secondary
;,~,:j absorber in the FCe gas plant. This material has a lower molecular weight than the light
cycle oil and is a better absorbing medium for the secondary absorber than the light cycle
oil. The heavy naphtha draw temperature is 34010 390 degrees F (171 to 199 degrees q
and this material distributes between the unstabilized gasoline and the light cycle oil
when it is not withdrawn from the column as a net product.

The main fractionator column shown in Figure 11.2 has both a top pumparound cooler
and an external reflux stream from the overhead condenser. Some designs do not have
external reflux from the overhead condenser to the main rractionaior, but rather totally
rely on the top pumparound cooler to generate all of the top reflux. However, the
majority of main fractionators have both top coolers and external reflux from the
condenser. The reactor effluent contains a large quantity of water and it is necessary that
the column overhead temperature be kept sufficiently high that all of the water leaves in
the overhead vapor from the column. Typical overhead temp.eratures for main
fractionators are in the range 290 to 32S degrees F (\44 to 163 degrees C).
:i
There are usually two stages of cooling for the main fractionator overhead with a set of
air coolers followed by water coolers to trim to the desired outlet temperature. The
overhead liquid product is unstabilized gasoline and it contains large quantities of light
gases that must be stripped in the FCe gas plant. The vapor product is the wet gas, and it
contains significant quantities of light hydrocarbon liquids and gasoline that must be

---
absorbed in the FCC gas plant. The wet gas is usually compressed in a massive t~- .
stage compressor to approximately 200 psig (14.8 bars) for processing in the FeC gas
plant. The unstabilized gasoline is pumped to theFCC'gas plant and used for lean oil in .
the primary absorber.

-- ----------,.,-"

f
'."
r.imter J1 211

nn."."t;c,n of the main fractionator requires maintaining an acceptable balance between


ctuties fouhe slu'!)' quench and the overhead condensers. The-,intermedia~_C90ling
dutL~s at Jhe,heavy'cyCteoif'and heavy naphtha ptimparounds are of much s~aller
magnitude and are. relatively fixed by their services in the downstream reboilers.

Refiners in cold climates may "swing" the separation between the gasoiine and light
cycle oil seasonally. In summer, the end point of the gasoline is raised to maximize
gasoline production. In winter, the heaviest portion of the gasoline is "undercut" into the
light cycle oil to maximize production of heating oil.

11.1.2.3
Slurry Strippers
The terminology for the bottom product froni' the main fractionator can be confusing
without some historical understanding. This stream has some suspended catalyst ftoes
and is therefore correctly described as slurry. The portion of the slurry that exits from the
process has historically been processed in a settler (or clarifier) where the catalyst fines
are at least partially removed. The catalyst fines are combined with a slip stream of fresh
feed and recycled back to the reactor. The settled oil is usually called clarified oil or
decant oil.

Early designs used a small steam stripper to strip light cycle oil and traces of gasoline
from the slurry product. The stripper overhead was routed back to the bottom of the main
fractionator for recovery of the light cycle oil and gasoline. However, these stripper
columns w~re difficult to keep in operation because of plugging of the trays with catalyst,
and nearly all have been removed from service.

According to Sadeghbeigi", improvements in the physical properties of Fee catalyst and


in the reactor cyclones have lowered the catalyst carryover sufficiently that many Fee
units now operate without catalyst settlers. Instead, the net bottom product from the main
fractionator is sent directly to storage. For refineries operating without settlers it is
necessary to remove catalyst fines from the storage tanks at some time ipterval. It is also
common for these refiners to use the terminology decant oil or clarified oil for the
unsettled slurry product.
.. -
212 FCC ProcesseJ

11.1.2.4
Fee Gasoline Splitters
In the years of large horsepower automobile engines and high octane premium gasoline,
it was common for refiners to split the full range FCC gasoline into light and heavy
portions. This,,,,as.easily accomplished with a splitter tower with 20 to 2S actual trays
operating at a low pressure and minimal reflux. The heavy FCC ga,oline was used in the
lower octane regular gasoline blends and the light FCC gasoline was used in the high
octane premium gasoline. The light FCC gasoline was rich in CS and C6 olefins and
when blended with catalytically reformed gasoline (high in aromatic compounds) the
blended gasoline had a higher than expected octane number. This synergistic effect.
reduced the need for octane enhancers such as tetraethyl lead and increased the :
profitability of the refinery.

The practice of splitting FCC gasoline was largely abandoned when the automobile
horsepower race was ended and the demand for high-octane premium gasolines
'I decreased. Times change, and the current interest in reducing the olefin content of
I! '.
gasoline for environmewal considerations has revived the practice of spiitting FCe
I!'
I1 gasobe. The light FCe gasoline is now reacted with metr.a'lol over an ion-exc!;
" catalyst to produce teniary amyl methyl ether (TAME). About 90 percent of the
methyl-butene-! and 2-methyl-butene-2 are converted to TAME in a two reactor process. :
The 3-methyl-butene-1 isomer does not react. See Section 10.1. 7.2 for IllOfe information:
on the TAME process.

11.1.2.5
Fee Gas Plants
Figure 11.3 presents a typical FCC gas plant. The wet gas from the main tractl()na.tor:
overhead drum is compressed in two stages of compression, cooled, and charged to
high pressure separator. The vapor from the high pressure separator is charged to
primary absorber where it is contacted with the unstabilized gasoline "lean oil" from
main fractionator overhead drum. r

The vapor product from the primaf)' absorber is charged to the secondary (sp'onl~eJ.
absorber where it is further scrubbed by contact with a lean oil stream drawn from
main fractionator. This lean oil stream is commonly light cycle oil or heavy n~rlhtlla:
The rich oil from the secondary absorber is recycled to the mai~ fractionator for rec:ov'lrv
of the absorbed gasoline and light hydrocarbon liquids. The tail gas from the sec,ondlary
absorber usually goes into the refinery fuel system.

The primary absorber bottoms are recycled back to the high pressure separator cO()lers..'
The liquid from the high pressure separator is pumped and charged to the <tril~Oel
(deethanizer) where C2's and H 2S are stripped into the overhead. The stripper nv.:rheall
is also recycled back to the high pressure separator coolers. The stripper bottoms
II 213 ,

ihalrged to the stabilizer (debutanizer) where the C3 and C4 hydrocarbons are remov!ld in
overhead product The stabilizer bottom product is full boiling range FeC gasoline,
As previously discussed, some refiners charge the full range gasoline to a splitter to
produce a light FCC gasoline for premium gasoline blending, or for charge to a TAME
unit where many of the CS olefins are converted to TAME .

.. Figure 11.3
Typical Fee Gas Plant

wash H20 Wash H2O


lean Oil r-~'" TailGn
(,om
Inlercooler Aw Main Frac.
Main Frac. ~, Serondary

Ovemead Absorber

Rich Oil
Overhead L...,i\Lo-O to Maio fide.
Drum Tri.m
Cooler

Reflux 10
Drum

Main frac. Unslabilizod Primary


Gasoline Absorber

/I ='ecy,1e High Pres.sure


Separator Drum

CO
Hydrocarbons

Splifter Stabilizer

C4 H,tdrocarbons Fee Gasolirie

The gas plant in Figure 11.3 has a splitter tower to separate the C3 and C4 hydrocarbons.
This tower is only necessary when the C3 and C4 c1efins are to be processed separately.
Note that it is necessary to treat the gasoline and C31 C4 hydrocarbon streams to remove
acidic compounds prior to their use as blending stock or charge to other processing units.
Refineries use a variety of amine and caustic solutions to remove the acidic impurities.

It is necessary to inject wash water into the wet gas compressor discharge to reduce
corrosion and keep salts in solution. The FCC feed stock contains low concentrations of
sulfur and nitrogen compf)unds which produce H2S, S02, HeN, and NHJ in the cracking
process The reactor a~d stripping steams create a wet environment in which the sulfur

i
I

i
214 FCC Processes

and nitrogen compounds become corrosive. Therefore, most refiners use a continuous
water wash to retard the corrosion. There are two common methods for injection of
water wash: forward and reverse cascading. These are illustrated in Figure 11.4.

Figure 11.4
Injection of Water Wash in FCC Gas Plants

Forward Cascade Washing:


Fresh
Wash H2O 2nd
Trim
lntercooler Stage Air
-Cooler
Cooler
Main Frac.
Overhead
High Pressure
....._ 1 Separator Drum

to Sour
Wash H20
H20 Stripper
to Sour
' - - - - - H20 Slripper
I'
I!'
ii
Reverse Cascade Washing: Wash H20

2nd
Trim
1"lerCOOler SIogo Air Cooler
Cooler
Main Frac. Ch""9{!~r~N--,
Overhead

Main Frac.
Ovemead
Drum
High Pressure

t 10 Sour
H20 Stripper
Fresh
wash H2O
Separator Drum

There are many variations in the process flow for Fee gas plants, However, for gas
plants without refrigerated lean oils, the process conditions are very similar. For these
plants, the outlet pressure from the second stage of compression ranges from 190 to 225
psig (14.1 to 16.5 bars) and the outlets from the water coolers are typically in the range of
,I 90 to 105 degrees F (32.6 to 40.9 degrees C). The primary ahsorber rides off the high
pressure separator drum and the secondary absorber rides off the primary absorber. The
, ,,
~ -,
high pressure separator liquid is pumped to the stripper which commonly operates in the
range 200 to 225 psig (14.8 to 16.5 bars). The stripper bottom product pressures into the
debutanizer which usually operates in the range lOO to ISO psig (7.9 to 11.4 bars). The
., debutanizer overhead is pumped to the e3! e4 splitter which operates at about 250 psig
I
I' (18.3 bars).

, ;

!!, ;
215

~R1ary' absorber often has an 'inten:ooler in the middle of the column to remove
the heat of absorption. The overhead from the primary absOlber is typically at
llO degrees F (40.9 to 43.7 degrees C) and the bottoms at 115 to 125 degrees F
to 52.0 degrees C).

stripper overhead ranges from 120 to 130 degrees F (49.2 to 54.8 degrees C) and the
'Stripl>"er bottoms is typically 320 to 350 degrees F (160 to 177 degrees C). The stripper
also have a water draw toward the top to remove free water that condenses in the

high pressure separator drum temperature is a natural control point for the Fee gas
'IP"'" If this temperature is too high, the absorber will be o\l.tertoaded. If this temperature
'is..tOO~low, the stripjler will be overloaded. For many non-refrIgerated' plants, the ideal
operating temperature-ranges from 90 to 109 degrees F (32.6 to 38.1 degrees C).

The stripper bottoms temperature is an important control point for maximizing propylene
recovery in the gas plant. Ideally, the stripper should remove most of the ethane and H 2 S
while minimizing the loss of propylene into the stripped vapors. Many operators tend to
strip alI of the ethane from the bottoms product (unstat.ilized gasoline). By leaving a
very small residual of ethane in the stripper bottoms, the overall re.:overy of propylene in
th~ Fee gas plant can be significantly increased.

It is a well established fact that the absorption process is not a very efficient way to
recover light hydrocarbon liquids. This process has been used for many years in the
recovery of liquid hydrocarbons from natural gas and the absorber technology commonly
used in Fee gas plants corresponds to 1950's "ambient" oil gas processing technology
Natural gas processors have made several improvements to this technology to increase
recovery of liquids, and some of these improvements have been incorporated into Fee
gas plants.

One obvious way to improve absorption is to cool the absorption oil. Absorption is
exothermic and as hydrocarbons are absorbed from the gas, the temperature of the lean
oil liquid rises. As the temperature of the lean oil rises, the driving.Jorce for absorption
decreases. Hence, the placement of one or two intercoolers to remove heat from the lean
oil at intermediate points in the absorber column improves the performance of the
absorber.

The heats of absorption are highest for the lightest hydrocarbons which gives rise to the
practice of "presaturating" the lean oil with light hydrocarbons prior to its introduction
into the absorber. This scheme has been incorporated into the primary absorber for many
Fee gas plants and is illustrated in Figure 11.5. In this scheme, the lean oil is contacted
with the absorber overhead gas where light hydrocarbon gases are absorbed. The
resultant liquid! vapor mixture is cooled and separated in the presaturator drum with the
vapor going to the secondary absorber and the presaturated lean oil fed to the top tray of
the absorber. Note that this is equivalent to operating the absorber with a liquid feed into
, a top condenser system. . .

I,
I
216 Fee ProceSSles

Figure 11.5
Presaturating the Primary Absorber Lean Oil
Cooler
Gas to
Lean Oil U-----,r---.{ r--.J ~~ Secondary Absorber

Presaturator
'----,--,-.Y Dn.m

Primary
Absorber

intercooler ,
High Pressure
Separator gas

I:! Rich 0.1


li
'i
"

'I;1 -----'--
ji
It is also an established fact that ~low,molccular-weightlean oil will-zDsorb more light
hydrocarbons (particularly C3's) than a high molecular weight lean oiL Gas processors
userughinolecular weight lean oils for absorbers when propane prices are low because
they are less expensive and less absorber oil is lost into the off-gas product. When
propane prices are high, they use lower molecular weight lean oil to maximize recovery
of propane, Therefore, by using a stream of heavy naphtha from the main fractionator as
secondary absorber "sponge" oil, the recovery of C3 hydrocarbons (notably propylene)
will be higher than that achieved when using the higher molecular weight light cycle oil
for sponge oil.

Some FCC gas plants use refrigeration to chill the lean oil for the primary and secondary
absorbers. This increases the operating cost for the gas plant, but may be justified in
many cases by increa ,ed capacity. The two stage wet gas compressor.-is often the
"bottleneck" when expanding an FCC operation. When the lean oil to the absorbers is
refrigerated, it is possible to substantially reduce the pressure of the high pressure
separator drum and still achieve good recoveries of C3 hydrocarbons. This reduces the
wet gas compression requirement and allows increasing the flow for systems that are
compression limited.
ihaJlter JJ 2i7

. FCC Processes: Simulation of Existing Units


Most models for Fee processes are developed for trouble shooting and expansion of
existing operations. Development of a useful model requires both a good understanding
of the Fee process and a working knowledge of the unit being modeled. There are many
nuances in the flow sheets of Fee processes, depending on the original designer and the
modifications incorporated in subsequent expansions. The continued development of
catalysts has also resulted ill modifications to designs and operating philosophies for Fee
units.

In this section, a step-wise method for modeling Fee processes is presented. In general,
the steps should be followed in the sequence in which they are discussed. The principles
may also be applied to the design of new units.

11.2.1
Definition of the Reactor Effluent
The reactor effiuent for an Fee unit is rarely sampled and analyzed. It is a wide boiling
mixture of hydrocarbons, steam, and catalyst fines at a very hot temperature. Typical
conditions are temperatures from 900 to 1025 degrees F (483 to 552 degrees C) and
pressures from 20 to 35 psig (2.4 to 3.42 bars). Therefore, the composition is best
determined by combining the analyses for the individual products from the fractionation
plant.

The main fractionator processes all of the reactor effiuent and separates all products that
boil higher than gasoline These products include decant oil, net heavy cycle oil (if a~y is
drawn), light cycle oil, and heavy naphtha. The light cycle oil and heavy naphtha have
boiling point ranges that are easily analyzed with the standard ASTM D86 atmospheric
distillation. However, heavy cycle oil and decant oil have boiling point ranges that
require a different method of analysis. The heavy cycle oil may have a final boiling point
greater than 900 degrees F (483 degrees C) and the end point of the decant oil approaches
1200 degrees F (649 degrees C).

The heavy cycle oil and decant oil can be analyzed with the ASTM DI160 vacuum
distillation; however, these samples are seldom run on a routine basis. Refiners are
concerned about the loss of light cycle oil in the decant oil, and a few atmospheric
distillation points are sometimes run for the decant oil to measure the loss.

02887 and D28S7-extended simulated distillation tests may be used to analyze heavy
cycle oil and decant oil. These streams both have a significant content of heavy aromatic
compounds and the simulated distillations should be corrected for parafftn bias. If no
laboratory correction data are available, the corrections in Table 11. I may be used.
218 FCC Processes

Table 11.1
Simulated Distillation Corrections: Heavy Cycle Oil and Decant Oil

Heav~ Cycle Decant Qil


Weight % Di,:illed r>~2 F De~C DcgF DegC
10 0 0 0 0
30 + S + 4.4 +15 + 8.3
50 +15 + 8.3 +30 +16.7
90 +30 +16.7 +50 +27.8

Notes: Intermediate pOints may be interpolated from corrections given "above. The end point for decant oil
may be arbirrarily defined as J200 degrees F (649 degrees q and disrillarion probabiliry paper may be
used (0 smooth the curve.

If no distillation data are available for the decant oil, the TBP distillation may be
estimated with the data in Table 11.2. These data are approximate but will give a
reasonable sc"ccing point tor the model development. Note that the data in Table 11.2
correspond :0 units without slurry strippers in operation.

Table 11.2
FCC Decant Oil TBP Distillations

API Gravity -5.0 -2.0 +2.0 +5.0


---------------- ---------------. --.------.-- --------------.-
LV% DegF Deg C DegF ~ Deg F Ikg.l; Deg F Deg C
IBP 550 288 525 274 475 246 450 233
10 715 380 700 371 670 355 660 349
30 790 421 775 413 750 399 735 391
50 850 455 840 449 825 441 815 435
90 1010 544 1000 538 980 527 975 524
EP 1200 649 1200 649 1200 649 1200 649

Note: Dis[illation probability paper may be used 10 estimate intermediate points.

The unstabilized gasoline and wet gas products complete the definition of the
hydrocarbon products from the reactor. However, it is difficult to procure good samples
and analyzethese streams accurately. A better strategy is to determine the analyses and
rates for the gasoline and lighter products from a material balance around the FCC gas
plant Since the true reactor effiuent is required for the main fractionator model, it is
necessary to subtract any non-FCC feeds to the FCC gas plant from the gas plant
Jl 219

lprl[)UlJ"'~.
This may be easily accompl~hed by using a stream balance block as illustrated
Example 11.1.

To complete the definition of the reactor effiuent, the steam injected to atomize the oil
feed and the steam used to strip the spent catalyst must be added to the hydrocarbon
portion of the reactor effiuent. There may also be other small steam flows that exit with
the reactor product that must be included, depending on the process. T~e steam has a
significant' effect on the main fractionator heat balance and also affects the hydrocarbon
part~ Er.t:ssuf.esin..1h~.fr:act~oriaior. :rhererore;' an"accuiaie'-!otal-steam' flow is
important
.. for a!!..l!.c;S;ur.alJu!wWllcl!9nJltor model. .
----~-.

Example 11.1
Determination of True Reactor Effiuent"for FCC

Plant Information:
A model is being developed for an Fee main fractionator/ gas plant operation. Product
yields and laboratory data are available for the main fractionator products. The steam
flows to the reactor have also been determined.

Gas streams from a coker unit and a crude unit are fed to the first stage wet gas
compressor. A high pressure gas from a hydrocracker is fed to the high pressure
separator drum. Analyses and flow rates are available for the non-Fee generated gas
plant feeds and for the total gas plant products.

Problem Statement:
Determine the true reactor effluent and model the main fractionator/ gas plant process.

Solution:
I) Enter the main fractionator side and bottom products into the simulator using the flows
and assay data that are available.

2) Enter the coker, crude unit, and hydrocracker gas streams into the-simulator.

3) Enter the reactor steam and gas plant products into the simulator.

4) Add the main fractionator products, reactor steam, and gas plant products and subtract
the coker, crude unit, and hydrocracker gas streams to determine the true reactor effluent.
A stream balance block may be used for this purpose.

5) Set the temperature and pressure of the true reactor effluent to the observed values.

6) Begin the simulation with the main fractionator and the true reactor effluent. [n the
gas plant model, introduce the external feed streams at the appropriate locations to
reproduce the actualloadings in the Fee gas plant.
220 FCC rrot:esse.

11.2.2
Collection of Operating and Laboratory Data
The general rule is to collect any data that are available for the process. This will be very
helpful when cross-checking and reconciling the data. Inevitably, there will be bad data
that need reconciliation. The following operating data should be collected when possible:

- Gas oil charge to the unit


- Steam rates to reactor, main fractionator, and stripper(s)
- Wash water circulation rate to the overhead condensers and compressor coolers
- Charge rate for other unit feeds to the FCC gas plant (if applicable)
- Rates for all products leaving the main fractionator
I '
- Rates for all products leaving side stripper colurnn(s)
,
- Rates for main fractionator overhead'products
- Rates for all pumparound streams (net and total)
- Rates for all pumparound cooling streams '
- Rates for heating mediums to FCC gas plant reboilers
- Rates of all feeds and products for the columns in the FCC gas plant
- Pressures:
Reactor outlet
Main fractionator reflux drum
Main fractionator overhead
Main fractionator bottom
First stage compressor outlet
Low pressure separator drum
11
Second stage compressor outlet
High pressure separator drum
Reflux drums (stabilizer, C3/ C4 splitter*, FCC gasoline spliuer*)
Top tray (all gas plant columns)
Bottom tray (all gas plant columns)
- Temperatures:
Reactor outlet
Main fractionator reflux drum
Main fractionator overhead
Main fractionator draw trays
Main fractionator bottom tray
Side stripper bottom temperatures
Return streams for all pumparounds
Exit temperatures for all pumparound cooling streams
First stage compressor outlet
Low pressure separator drum
Second stage compressor outlet
High pressure separator drum
Reflux drums (stabilizer, C3/ C4 splitter*, FCC gasoline splitter*)
Top tray (all gas plant columns)
11 , 221 '~~

Bottom tray (all gas plant columns)


Reboiler inlet and outlet for stripper, stabilizer, C31 C4 splitter, and
FCC gasoline splitter*

The following laboratory data are recommended:

- Gas oil feed assay data: gravity and lab distillation


- Component breakdown for all gas plant feeds from other units
- Gravity aF.c\ lab distillation for: heavy naphtha, light cycle oil, heavy cycle oil,
and decant oil
- Lab distillation, gravity, and light ends breakdown for FCC gasoline
- Lab distillation, gravity, and light ends breakdown for light FCC ga~oline*
- Lab distillation, and gravity for heavy FCC gasoline-
- Component breakdown for C3! C4 and tail gas products

* when unit has C3! C4 and! or FCC gasoline splitter columns.

All temperature and flow data should be collected for the exchangers that heat the gas oil
feed to the reactor. This is helpful for reconciling the rate of the decant oil when decant
oil is in the preheat train. The gas oil feed rate is a more reliable rate than the decant oil
which is difficult to meter accurately.

A weight balance should be constructed around the process using the mass of the gas oil
feed, gas plant feeds from other units, and the main fractionator and gas plant products.
There should be a shortage in the product mass that is equal to the coke production. If
the material balance is in error by more than two or three weight percent after the coke
has been accounted for, the source of the imbalance should be located and corrected.
Arbitrarily normalizing the FCC product data is not an acceptable substitute for locating
the problem!

The following rates are likely to be inaccurate, especially if the meter factors have not
been updated: main fractionator reflux rate, pumparound rates, heating medium rates.
Note that these streams are not products and accurate rates are not needed for operations.

" FQ[ .mainJr:actionators, the temperature measureme.nt9r~h~_oyerhead vapor leaving the


'column tends to be .i.O.'!fl!rate. Interestingly, the measure.QJemlteJafure...ls lower than the
~ -. __ . _. _. ~_~ . _, __n__ '----
simll!ated._temp.@t.ure whenthere is a difference. One explanation is that liquid
I ent.@inment in the-over!!ead vapor causes a "wet bulb" effect-that lowers the measured
temperature. It is not unusual to have a difference of 15 to 25 degrees F (7.8 to 13.9
-
degre,es C) between the measured and simulated overhe<!.Qtemperatures.
- , ~~ -...~.'~.~-----..,

It is useful to cross-check the pumparound exchanger information. Most pumparound


exchangers do not have vaporization of the cooling medium and all heat transfer is
sensible heal. Therefore, the duty may be easily verified. Pumparounds with stea,m
generators arE, aI~.easily verified by comparing the steam duty to the hydrocarbon duty.
:1
-
222 FCC Processes "
t
Main fractionator product draw temperatures are usually reasonably accurate. depending
on the point of measurement. It is important to remember that the simulation model draw
temperature is the true bubble point of the liquid product at the draw tray pressure. For a
j ~

main fractionator draw that is fed to a steam side stripper. the side stripper bottom fee'.
temperature provides a cross-check for the main fractionator draw temperature. actl'i
bat 4Ij
co r _
The main fractionator bottoms Gre often sub cooled below the bubble point by injection of
anc --~!!
cold slurry quench into the column boot. This subcooling must be appropriately modeled
for agreement between the bottom temperatures of the model and the plant.

The reflux rates for the light hydrocarbon col,!mns in the Fee gas plant are not always
Th ;
str
1
accurate. The temperatures and the compositions of the products are the most accurate the.
at ':0
measures for the column operations.

11.2.3
11';
M'
Reactor l\104eling "

The re".'tion mechanism in the FCC reactor has been previously discussed in '1eetiOIl TI
10.1.1. Because of the complexity of the reactions and the inadequacy of pseudo- 11-
ml
components to represent chemical class. this rcact{)f must be represented by a "black
box" when using commercial simulation programs. pr'
tl;41
There are three steps involved in developing the reactor effluent as described in Figure m.
11.6. First, any external gas plGot feeds must be subtracted from the gas plant products to
determine the true gas plant products from the Fee reactor. (See Example 11.1.)
S,
t)
Figure 11.6
He
Black Box Model for Fee Reactor 5'.

I ElCtemaf
Feed .,
E:demal
Feed 11
Steam tl.
fi ;'

~;

Tail Gas ===:1 Stream Add


I
light Cyds 0i1

Heavy Cycle
.----------~
Decant O~
Oil Reacto<
Ma..
Hydrocarbon
Emuenl
~

Stream
Combine
t.-:e
C

c:rs and I Balance <


C4's
il
:.
Subtr.lict 1 True Fee Gas Plant
Products

I
l
C"".
(by DCfeumC4!l)
--,,
,,
,

Gas Plant
-- Reactor Effluent
10 Main
Fractionalor

Define Temperature
and Pressure
223

the true gas plant products plus the main fractionator products must be mass
against the fresh gas oil feed to the reactor. The difference in the mass of the
and the FCC products is the coke production. This should be checked against the
coke production. If the difference of the coke production predicted by the mass
IIIII~I""~ is greater than 2.0 weight percent, the source of the error should be located and
For errors smaller than 2.0 weight percent, the coke weight may be defined
the error normalized into the total hydrocarbon effiuent stream.

tf'lrd step is to add the reaction steam. This includes steam for atomizing the feed,
ili'?'clrinnl'nl! the spent catalyst, and other steams introduced into the reactor system. After
reaction steam has been added to the hydrocarbon effiuent, the resultant mixture is set
the reactor outlet temperature and pressure.

typical operation and control of the main fractionator has been discussed in Sec/ion
1.2.2 and a main fractionator is depicted graphically in Figure 11.2. In many ways the
fractionator is similar to the crude distillation tower, and the early catalytic cracking
.prclCe!;Ses labeled the main fractionator as the sylllhe/ic en/de or syn tower. The feed to
the main fractionator is similar to crude oil and consists of a wide boiling mi>.1ure with
),', ......."J components.

Similar to crude distillation, all of the heat input is present in the feed to the tower. Both
types of towers have side draws, side strippers, and pumparound cooling circuits .
. However, the main fractionator is different from the crude tower in that the feed is
.. superheated and must be "quenched" prior to fractionation. The feed to the main
fTactionator also contains a much higher percentage oflight gases and steam than the feed
the crude tower.
:1
I
Main fractionators contain from 24 to 36 trays, depending on the design, with early
designs having more trays than later designs. Functionally, the separatj;Jlls achieved in 1I
this column are relatively insensitive to the number of theoretical trays used in the model. .\
Typical main fractionator models use 12 to 16 theoretical irays to represent the
sc:llarations and heat transfer that occurs. Similar to the crude tower, the separations are
largely defined by the composition of the feed (reaGtor effiuent). Therefore, it is
impossible to overcome poor representation of the reactor effiuent with tray efficiency
adjustments.

In the discussion following, modeling of the various sections of the main fractionator are
fi;.ilis'::us,sed from the bottom of the column to the top.

r ..
-
224 FCC I'r()(:e~

11.2.4.1
Quench (Desuperheating) Zone
The quench zone of the main fractionator is depicted in Figure 11.7. A circulating stream
of cooled slurry is used to desuperheat the hot reactor effiuent in this zone. To prevent
cracking and coking in the column boot the slurry bottom product is cooled to the range
675 to 700 degrees F (358 to 371 degrees C). Most main fractionators have a direct
injec~ion of cool slurry into the column boot as shown in Figure 11.7. This insures that
the bottom product is subcooled below its bubble point.

Figure 11.7
Main Fractionator Quench Zone

Sloom
Vapor
ID.-cO
$urry
tI ,
Uc,Je
tom ><:0
j Ouench

S:eam Generators

Boiler Feed H2O

As&1or E"Us re

[)ecantOiI

F or column simulation purposes, the series of disks and donuts in the quench section are .
represented as two theoretical trays: a pumparound draw tray and a pumparound r"IUII.. ;
tray. Little fractionation takes place in this zone which is designed for heat transfer,
main fractionators with slurry subcool injection, an additional tray must be added to
represent the subcooling effect in the boot of the column. Since every tray must have a .
vapo~.a.!l.d liquid product, a dummy stream consisting of a smatlSl1Jantity of ';..ncoiidenslble.
g~~i~Jntr9~it:c~d}.s a feed to the subc(){)ling triif' - . ' .
. (

Figure 11.8 presents two possible simulation configurations for main fractionator quench
zones with slurry subcool injection. Scheme A uses two pumparounds and two
pumparcund coolers and is readily implemented in any commercial simulator without the ..
necessity of a recycle loop. The allocation of the cooling duty between the two
pumparound coolers is somewhat arbitrary, and there is no guarantee that the two .
pumparound return streams will be at the same temperature. However, this is a small.
assumption that is justified by the ease 'in solution of the model. The total of the two
pumparound cooler duties is the total heat removal from the slurry.

Scheme B is a true model of slurry subcool injection. For this scheme there is one
pumparound cooler, with the cooler outlet split between the quench zone and the

. . .----~ -- - -----. . _. ~---'--.-,--~


Jl 225

iec;tion stream. This scheme will yield the same total cooling requirement as Scheme
however, it is only recommended for commercial simulators which are able to solve
cool slurry split option simultaneously with the column equations.

Figure 11.8
Main Fractionator Quench Zone Simulation Configurations

Nl Nl
Sluny Reador Slurry r-{r-~...-o-l Reador
N Effluent N Effluent
Quench Quench
PIA PIA
Sub-
Cool Dummy Cool Dummy
PIA Feed feed
. .- - ' - - - - - - ' - -. . Decant Oil ....._ _ _ _ _-1.-0.. Decant Oil

Scheme A: 2 Pumparounds Scheme B: Split Pumparound Retum

The simulator considers only the net heat transfer to the slurry quench and subcool
streams, i.e., only the duty that affects the column. The true slurry heat transfer circuit
must be built outside the column model by using column "internal" streams to reconstruct
the total bottom flow. In the external model of the slurry cooling circuit, the heat
transferred to the column must be equal to that calculated in the column model. For
Scheme B, this is easily accomplished by defining the external circuit return temperature
at the value determined in the column calculations.

For Scheme A, the average temperature of the two column pumparound return streams
may be determined by adiabatically combinirig these streams. This temperature may then
be used as the return temperature for the externally defined slurry return stream to insure
that the heat transferred to the column in the external circuit is identical to that
determined in the column calculations.

11.2.4.2
Heavy Cycle Oil Zone
The heavy cycle oil zone is the zone of the column between the heavy cycle oil
PUmparound return tray and the column quench zone. The liquid flow from the bottom
Iray of this zone is usually the lowest liquid flow in the column and this tray is somewhat
analogous to the flash zone in the crude distillation column. This entire zone is
I
characterized by large vapor flows and low liquid flows, resulting in low actual tray
The zone is more for heat transfer than for fractionation. Ii
;
------------------------
,,,.-,,
- .4

226 FCC Processes

A main fractionator heavy cycle oil zone and the ~rresponding simulation configuration
are shown in Figure 11.9. Regardless of the number of actual trays between the heavy
cycle oil draw tray and the slurry quench return, one theoretical tray is adequate to
represent the separation in this region. The heavy cycle oil pumparound section may be
represented with a draw tray and a return tray. On occasion, including an additional tray
! between these trays may result in a better match to the plant data, Note that the
ij!
,1" pumparound section is primarily heat transfer, regardless of the number of actual trays in
this section,

Figure 11.9
Main Fractionator Heavy Cycle Oil Zone
I VapOf Liquid
'I.

II
Vapor liquid to LeO from LeO
10 LCO from LCO

P/ARelum

HCO
Exchangers
II.fHcol
PIA

----- EXChang:J
I' ,,
Heavy .."..--
Cycle Oil
-TI
__ ~
I ,,, t+
Vapor liquid
-,-:j

Heavy fr Quench to Quench


Th4
Cycle Oil
tra
Actual Configuration Simulation Configuration
tra
tCj
sec
j
Observe in Figure 11.9 that the pump-back heavy cycle oil to the tray below the draw
tray plus draw tray overflow (if any) is represented by the tray net liquid leaving the draw . Tb"
fia<~
tray in the simulation configuration.
~
In similar fashion to the slurry heat transfer circuit, the total heavy cycle oil Jiraw from rep
the column must be reconstructed from column "internal" streams so the true heavy cycle
oil pumparound cooling circuit may be represented externally. There are typically l~
several exchangers in this cooling circuit, often including the stabilizer reboiler. To
insure that the external circuit is in agreement with the column calculations, the heavy
H~
cycle oil return temperature in the external circuit must be set to the value determined in Th~
the column calculations, typl
thd
11.2.4.3 pro',
Light Cycle Oil Zone 'ast!
Witl
The bottom of this zone is defined as the tray above the heavy cycle oil pumparound
return tray. The top of the zone is the top tray of the main fractionator for columns with
------------------...... ;,c:';.:r,~\~:W~~!t,~:{i>}E:~;~: 't, ;

-;haJ~ter 11 - '22t"'!X

heavy naphtha coolers. For columns with heavy naphtha coolers, the top of the zone
is defined as the tray immediately below the heavy naphtha draw tray:

Figure 11.10
Main Fractionator Light Cycle Oil Zone

top reflux
or liquid from
hVy naphtha
I
"
fto condenser
or heavy naphtha
zone
zone

~----o Rich OH Return N+4 f+-----o Rich OU Return


--r--l~.. lean Oil N+5 ~--I~"Le.n Oil

N+6
N+7
L .....- - - { J Steam LJ.oI~--{J Steam
LL:-r--- Ught Cyde Oil
to heavy I ffrcm heav LL--r.... light Cyde Oil
cycle zone , I Y
eye e zone

Actual Configuration Simulation Configuration

The light cycle oil zone is illustrated in Figure 11.10. There are typically 8 to 11 actual
trays above the light cycle oil draw tray and 3 to 4 trays below the light cycle oil draw
tray. The light cycle oil is steam stripped for flash point control in a steam stripper with 4
to 6 actual trays. A portion of the light cycle oil draw is split and pumped to the
secondary absorber as lean oil, with the rich oil returning to the main fractionator.

The simulation configuration shown in Figure 11.1 0 is adequate for most main
fractionator models. Five theoretical trays are used above the lean oil draw tray and two I
theoretical trays are used below the lean oil draw tray. Two theoretical trays are used to I
represent the light cycle oil stripper. I
~I
11.2.4.4
Heavy Naphtha Zone
The heavy naphtha zone and overhead system are shown in Figure I LIl .. There are
,
typically 5 to 7 trays in this zone when it is present. It may be represented with three i
theoretical trays. For some operations, a heavy naphtha may be withdrawn as a net I(
product. Some FCC gas plant designs withdraw a small stream of heavy naphtha for use '/
as lean oil in the secondary absorber. The rich oil return is usually returned to the column
. with the top reflux flow. ,I
1r
!i

mn "internal streams" should be used to re<:onstruct the heavy.naphtha circuit


to the column m()del.
e)Cf"rn,,1

228 FCCPr"'....

Figu re 11.11
Main Fractionator Heavy Naphtha Zone and Overhead System

H20 Coolers
Actual Configuration Air Coo\o;;r
~ _ _ _ Wel G;;.~ 10

Heavy Naphtha Gas Plant


Lean Oil Return 0-------,
Heavy Naphtha
RefkJl!;
10 ~oduct Of loan uil
Sour Water
Unstab.
Heavy Naphtha ,....,r-1~Gasoline to
Pumparound Gas Plant

I irmm I"hl
to light + cycle zone
eye'" zone

Simulation Configuration
~ _ _ _ WetGa$IO
i-,_: ,,"y Naphth.! Gas Plan!
L~"I, Oil Retufll
0-------,
Heavy Naphtha
to product or jean-oi
s..._
Heavy Naphtha
-'-
2 Un$Iab.
Gasoine to
Pumparound
3 Gas Plant

11.2.4.5
Overhead System
A typical main fractionator overhead system is shown in Figure 11.11. There are ...... ~ .. J."
at least two sets of condensers in series, with the first set being air coolers and the sel::0I1d
set being water coolers for trim cooling of the condensed products. Wash water
circulated back to the inlet to the air coolers to dilute the corrosive compounds in
overhead vapor and reduce corrosion.

The simulation configuration is also shown in Figure 11.11. All simulator pnDgl-arr1S
consider only one heat sink for the condenser. Pumps are also ignored since they have
effect on the distillation calculations. It is necessary to build a sub-model outside
column to include all of the condenser details. This may be accomplished by
the top tray vapor outside the distillation model and building the overhead system
pumps, exchangers, separator drums, etc. When a detailed condenser configuration
Jl 229

outside the column model, it is recommended that the reflux drum temperature and
the reflux flow, and the wash water flow be defined identical to the values in the
:P[l:SSLIIC;,
. column model.

11.2.5
Gas Plant Columns
Typical Fee gas plant operations have been discussed in Section 11.1.2.5. The wet gas
is compressed in a two-stage compressor with cooling and separation following each
stage. The vapor from the high pressure absorber is charged to the primary -absorber and
the liquid is charged to the stripper. Typically, unstabilized gasoline from the main
fractionator overhead drum is used for primary absorber lean oil. The primary absorber
bottoms and the stripper overhead are recycled to the high compression stage coolers.

The liquid from the stripper is stabilized by removal of the e3/ e4 components. The
vapor from the primary absorber is charged to the secondary absorber where It IS
contacted with a lean oil stream drawn from the main fractionator. The rich oil from the
secondary absorber is returned to tne main fractionator.

Sulfur and nitrogen compounds are corrosive in the wet environment in the gas plant.
Therefore a water wash system is used for the compressor discharges to reduce the
corrosive effects. Water wash systems are illustrated in Figure 11.4.

The sections following discuss modeling techniques for the various gas plant columns.

11.2.5.1
Primary Absorber
The primary absorber commonly has 30 actual trays. There are no heat sources, but there
may be one or two intercoolers to remove heat from the column. From a modeling
standpoint there are no degrees of freedom for this column and therefore no performance
specifications are allowed. r

An overall tray efficiency of 20 to 30 percent is reasonable for these columns. The


intercoolers may be represented as heat sinks that remove heat from a column tray_ It is
not necessary to model the intercooler liquid flow from and to the column.

Some Fee gas plants feed the primary absorber lean oil to a presaturator circuit as
illustrated in Figure 11.5. In this scheme, the lean oil is combined with the absorber
overhead gas, cooled, and the presaturated lean oil is returned to the top tray of the r
absorber. This configuration may be represented with a refluxed absorber model. For the I
refluxed absorber there is one degree of freedom, the condenser duty. An appropriate
performance specification is the temperature of the reflux drum.
230 FCC Processes

It is not UIlCOIIIIIIClIl for primary absorbers to have some wl!-ter condensation below the
intercooler(s}. In a plant environment, the small traces of water leave with the column
products. For simUlator distillation calculations, the presence of free water can cause
calculation diffio.I1ties. There are two ways to solve these difficulties: add a water side
draw below the i.tclercooler tray(s), or simply remove enough water from the column feed
that the free "'i:ef problem disappears. The latter method may be used for any
commercial si:::t:l:mx t<ith only a minor effect on the results. The former method of
adding a side W;:=~ ':':-aw may not be available for all commercial simulators.

11.2.5.2
Stripper
FCC gas plant ~;';:= commonly have 24 to 30 actual trays. There mayor may not be a
water draw nez:o :.':e tOP of the column to remove free water. The column has a reboiler
that absorbs he,;.: from other process streams in the Fee complex. Stripper reboilers may
be reboiled \\~-;.:. one or more of the following streams: heavy cycle oil, light cycle oil,
heavy naphtm.. a::c'or S'"cabilized Fee gasoline.

An overai; t",:.- e::~c c::JCY of 50 percent is reasonable for these colu;r.ns. Thc: reboiler
heat input allo';,-; ,C~ performance specification in the model. Any of the following
performance >~o:-~i::~,,-::ons may be used: reboiler temperatuce,bottom tray temperature,
ethane cont= "f the Stripped liquid, ethanol propane rarioin the stripped liquid, and
overhead terr:~_=e Specifications of the stripped liquid composition are desirable,
since they ace :::ce;:c.cent of the reboiler representation. .

For strippers '.".-_~. fr:, water, there may be simulation problems as previously discussed
for primary a:,<-':~ V;~ter draws, if present, may be modeled as side water draws for
simulators wi::: ::;< ~ability. For simulators that do not have this capability, the water
may be remo.~,: ::-0::-. tc'le stripper feed with negligible effect on the calculated results.

11.2.5.3
Secondary Absorber
4
1 Secondary a: ~:c~ -:::.ay have from 12 to 24 actual trays. There are no heat sources or
siriks. Tr,~~:ce. :::ere are no degrees of freedom available for performance
specificati~c.;

Overall tra:; e:::::e:::::es are commonly 20 to 25 percent for these columns.


This tower removes the e3 and e4 hydrocarbons from the Fee gasoline. It is sometimes
called the debutanizer tower. Stabilizers typically have 34 to 38 actual trays and operate
with overall tray efficiencies in the range 75 to 80 percent.

The fresh feed is pressured into the stabilizer from the stripper, and is introduced in the
middle of the column. These columns have both condensing and reboiling systems,
resulting in two degrees of freedom. This allows two performance specifications to be
used to describe the operation.

One specification should define the light material in the bottom product .. Any of these
specifications may be used: gasoline RVP; fraction n-butane in the gasoline, reboiler
temperature, or bottoms temperature. Typical stabilized gasoline has an RVP in the
range 5.5 to 6.5 psi (0.38 to 0.45 bar).

The second specification must define the heavy material in the overhead product. Any of
the fol!owing specifications may be used: fraction i-pentane in the overhead liquid,
column overhead temperature, top reflux rate, or top reflux ratio. The condensed product
is usually subcooled; therefore, the condenser outlettemperature is not a satisfactory
specification for the heavy material in the overhead product. Typical reflux ratios (LI D)
for debutanizers are in the range 1.5 to 2.5.

11.2.5.5
C3/ C4 Splitter
Some Fee gas plants separate the e3 and e4 hydrocarbons by pumping the stabilizer
overhead product to a splitter column. Since propane is removed in the overhead
product, this column is also called the depropanizer.

C3/C4 splitters commonly have 34 to 40 actual trays, with the feed introduced about mid-
column. A typical overall tray efficiency is in the range 75 to 80 percent Since the
column has both reboiler and condenser systems, there are two degrees of freedom for the
calculations. Two performance specifications may be used.

To define the light material in the bottom product, the following specifications may be
used: fraction propane, reboiler temperature, or bottom temperature. For definition of the
heavy material in the overhead product, the following specifications are available:
fraction i-butane, column overhead temperature, top reflux rate, or top reflux ratio. The
condensed product is usually subcooled; therefore, the condenser outlet temperature is
not a satisfactory specification for the heavy material in the overhead product. Typical
reflux ratios (U D) for e31 C4 splitters are in the range 2.5 to 3.5.

.- ':,~._ " I ',I


232- FCC r rn,,,,,.<~

11.2.6
Recycle Loops -
There are at least three recycle loops in an Fee gas plant configuration. The loops may ,
be grouped into inner and outer loops. F9f successful con"ergeDce of this "nested" :: .
re<;):.cle..5Stem,-the.tole~<!!L~~~_.the inner 100~atio.nUI!J.1.st_bJ!..smaJleUhan those
for the out!';r.lo.Qll_For the Fee gas pliiiiCihcouter loop is always the loop between the
s~condary absorber and the main fractionator.

There are two inner recycle loops that should always be solved simultaneously, since
-are inter-dependent. These ate the primary absorber bottoms recycle to the high pressure
coolers and the stripper overhead to the high pressure coolers. Since both of these.:
recycle streams feed back to the same flow sheet unit operation, they may be combined in
a stream mixer, with the mixer product fed back as the recycle stream. This scheme has
the advantage of representing the inter-dependency of the individual recycle streams,
while reducing the number of recycles from two to one. The disadvantage of mixing the
two high pressure cooler recycle streams is the difficulty of estimating an initial
composition and flow for the comt'ined 110',',' to initiate the recycle calculations.

Occasionally, an Fee gas plant may have a recycle of stahilized gasoline bac c: to the
primary absorber as top absorption oiL When present, this recycle loop should be solved
simultaneously with the other two inner recycle loops previously discussed.

11.2.6.1
Recycle Estimates
T;) solve an Fee main fractionatorl gas plant system it is necessary to provide some
estimates for the recycles. For the main fractionator, the rich oil return from the sp<mg1e.Jo
absorber may be estimated by supplying the lean oil composition and flow. The
ends pick up in the secondary absorber is small and may be ignored for the first loop
calculation. Supplying this recycle estimate insures that the main fractionator is in"
reasonable material balance when the lean oil stream is withdrawn as a side product.

It is necessary to supply an estimate for the primary absorber rich oil return to the high
pressure separator drum for successful solution of the stripper column. The stripper
overhead vapor recycle stream is relatively small and may be ignored for the first loop
trial for the inner loops. For com~ercial simulators that ~re truly interactive, this can be
accomplished by supplying zero estimates for the rich oil and stripper overhead recycles,
marking both the outer and the inner recycles as inactive, and then calculating the
primary absorber. The dummy primary absorber rich oil stream may then be replaced
with the calculated stream and the inner recycle loops marked for solution. Upon
solution of the inner recycle 100ps, the outer recycle loop may be marked for solution.

c
c
~~~$.~it:-''fWi.ij1{~~~.~''!i1;Tt.~c~ ;,::,\:,~:fS'r.'i~)~j('i!~t:9~~~~At,,~~t\Si;? /i,,~~~iii"". "r co.c,.,,
,
Chapter 11 233

11.2.7 -
Solution Techniques: Inside! Out Column Algorithm
The Inside! Out (I/O) column algorithm is very effective for main fractionator and Fee
gas plant columns .. Iteration variables include the tray temperatures, tray flows and
compositions, tray heat balances, and tray vaporlliquid equilibrium relationships. Main
fractionator side columns and pumparound circuits are solved simultaneously with the
main column trays by this method. The tray pressures are supplied by tlr<! .model builder,
and will not be changed during the solution process. The solution is based on
performance specifications that are supplied by the user and! or by program defaults ..

11.2.7.1
Initial Estimates: Main Fractio'nator
The solution procedure is iterative in nature and starts from estimated temperature, flow,
and tray compositicn profiles. The procedure is robust and most calculation failures are
the result of badly chosen performance specifications. However, the solution process
may be expedited by furnishing reasonable estimates.

In particular, convergence is enhanced by good estimates for the main fractionator


temperature profile. For main fractionators the following temperature estimates should
be provided: reflux drum, column overhead, all product draw temperatures, and column
bottom.

As previously mentioned, the rich oil return to the main fractionator from the secondary
absorber should also be estimated and supplied to the model. It is not necessary to
estimate the light ends pickup from the secondary absorber, but the lean oil portion
should be supplied to insure that the main fractionator is in material balance for the first
outer loop trial with the gas plant.

The I/O method is relatively insensitive to the estimated column flq,ws. However, it is
good practice to provide reasonable flow estimates for the overhead reflux and all
products for which the rates are not specified.

11.2.7.2
Initial Estimates: FCC Gas Plant Columns

For the primary and secondary absorber columns, only the top and bottom tray
temperature estimates need be supplied.

For the stripper, the top, bottom, and reboiler temperatures should be estimated.
Optionally, the flow rate of the overhead gas may be supplied. For the stabilizer, e3! e4
splitter, and Fee gasoline splitter the following temperature estimates'are recommended:
!
1
234 FCC Processes

condenser drum, overiJead, bott9tn, and reboiler. While not essential, it is good practice
to estimate the top rc:iux flow. An estimate for the rate of the overhead product is also
suggested.

11.2.7.3
Initial Model Phase
The main fractiona:;x should first be solved and the data reconciled before proceeding to
the gas plant calcuiz::cns. Trle answers will change slightly when the FCC gas plant is
added and the seconry absorber light ends are introduced into the calculations.
1

The following sel L': s:ccificalions is recommended:

Heavy napr.:'4 light 2nd heavy cycle oil pUlTIparounds: circulation rate and delta
teiT~.:.:ure

Slurry que!1= ""d subcool pumparounds: circulation rates


Draw rate, c :et he2:y naphtha, stripped light cycie oil, net heavy cycic oil, lean
oi!

Draw rate fx =CC2ll1 oil


.1

Top reoyC:~ ~=

Bottom te'::-':"-,":'.lre fc~ columns with subcool injection

Condense:- :~p!rature
;i
:1
For this set of ~-"'catior.5, the degrees of freedom are the flows of the wet gas,
~1
:r= unstabilized gas: .:x .:raw 10 the light cycle oil stripper, the overhead condensing duty,
,:(
the duty for the ;.:.:c-:' ~uen:r, pumparound, and the duty for the subcooler pumparound
(if present). It;, .-::'.1lanl :::2.t the three duties mentioned above are always degrees of .1
1 freedom for the ~,"-,aiions.

11.2.7.4
Tuning the ~bjel

The premise fo~ =: ;ection is that the major data problems have been resolved in the
initial model bu::=-~~ :nase fur the main fractionator. The model can now be made more
general and tunt'::

For the main frE:-;:,:;:aror, the oe"-.-ant oil flow rate may be replaced with a specification
for the top of W ::::iumn. The following specifications may be used for this purpose: .

I,
I"
I;

~
';htzj7ter 11 235

(x,llulTm overhead temperature or D86 95 pecceot distilled for the unstabilized gasoline.

'. The duties used in the main fractionator for the heavy' naphtha, light cycle oil, and! or
heavy cycle oil pumparounds shouldhe checked and adjusted as needed. Since there are
often "trim" duties in these circuits, it is not necessary to tie the main fractionator duties
directly to the sum of the calculated duties.

The main fractionator overhead condensing duty and total quench! subcooling duty
should always be calculated. Ihhere is a serious discrepancy with the plant data, the
source of the discrepancy should he located. For reconciliation of the slurry flow rate
(and duty), the preheat exchanger(s) witb fresh gas oil feed are very helpful. The flow
rates and temperatures for the fresh gas oil feed are usually more reliable than the rates
and temperatures for the slurry.

References:

78 Sadeghbeigi, Reza, Fluid CatalytiC Cracking Handbook, p 21, Gulf Publishing


Company (1995).
-:; -

12.0
Catalytic Reforming Processes
The reforming of naphtha feed stocks over platinum catalysts was pioneered by
Oil Products, with the P/atjorming process introduced in 1947. There are
licensed reforming processes in operation today that use platinum-based cataly:st;
produce aromatic compounds as well as high octane gasoline blending stock.
catalytic cracking, the purpose of reforming is not to crack the feed stock, but