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Contents
Introduction
Feedstocks properties
Naphtha hydrotreating kinetics
Naphtha hydrotreating hardware
Pitfalls in naphtha hydrotreating
FCC naphtha processing
Coker naphtha processing
Introduction
Naphtha hydrotreating is found in every refinery
Naphtha feed to reformer must be very low in sulfur
Naphtha can be treated to upgrade properties for
gasoline blending:
Light coker naphtha
FCC naphtha
Steam cracked naphtha
NHT
Isom
GASOLINE
NHT
CRUDE
Reformer
CDU
Jet/Diesel HT
HCPT
DIESEL
HC
LCOHT
VDU
FCC
FCCPT
Coker
Coker
NHT
FCC
NHT
Naphtha
C4 - C11
C4 - C6
Isom
I-C4 N-C4=
Alky
C7 C11
Reformer
Isomerization
Converts straight chain parraffins to branched
isomers
Increases Octane
Alkylation
Reacts Isobutene with N-Butane to form Isooctane
Very high octane
No contaminants
Reforming
Reforming converts paraffins and naphthenes into
aromatics
Increasing octane
Hydrogen as a byproduct
Sulfur
Nitrogen
Arsenic
Lead
Water
Silicon
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C ru d e
B re n t
D e n s it y
0 .7 6 9
P + O /N /A
4 2 /3 4 /2 4
A r a b L ig h t
350
0 .7 4 2
6 5 /2 0 /1 5
A bu Dhabi
600
0 .7 4 7
6 5 /2 0 /1 5
B e rri
500
0 .7 4 6
6 5 /2 0 /1 5
B o n n y L ig h t
500
0 .7 4 6
6 5 /2 0 /1 5
M aya
400
W TI
200
N o r th S lo p e
130
4 0 /4 5 /1 5
8000
5 5 /3 2 /1 3
L lo y d M in is t e r
10
S u lf u r
30
6 0 /2 7 /1 3
0 .7 5 7
4 8 /4 5 /1 2
Diene
(g/100ml)
Sulfur
(ppmw)
Nitrogen
(ppmw)
High Sulfur
90
15,000
500
Low Sulfur
80
1,000
200
High Sulfur
90
>5
10,000
1,000
Low Sulfur
80
2,000
450
FCCU
50
<0.5
1,200
100
Resid Hydrocracked
20-100
50-200
Origin
Visbreaker
Delayed Coker
11
Feedstock Summary
Often applied before processes that increase the
octane of the gasoline
Downstream processes based on Noble metals
These require very low S and N levels
Often < 0.2 ppmwt S and N
CF
k = LHSV ln
CP
Where k = rate constant, LHSV = space velocity, C =
Concentration of reactant of interest (e.g., S, N)
13
HDO
ln(Co/Cp)
5
4
3
HDN
1
0
0.0
0.1
0.2
1/LHSV
14
0.3
0.4
mercaptan
sulfide
disulfide
thiophene
5 Nm3/m3
10 Nm3/m3
8 Nm3/m3
20 Nm3/m3
60 Nm3/m3
45 Nm3/m3
1.3 Nm3/m3
2.5 Nm3/m3
4.2 Nm3/m3
Mercaptan Recombination
RSH
+H2
-H2
R=CH2
S
2
-H
S
2
H
-
+H
+H
S
2
R-CH3
Olefins and H2S can form mercaptans which increase the total
HDS activity requirement
Olefins can either be present in the feed or created by
cracking reactions near the reactor outlet
This becomes significant above 340 C
1 to 10 ppm additional S in product from this type of recombination
16
Kinetics Summary
Naphtha treating is a vapor phase reaction
HDS and HDN are first order reactions in naphtha,
but HDN is much slower than HDS
Hydrogen partial pressure is important
Function of recycle gas circulation rate.
17
Catalyst Selection
Relative level of sulfur and nitrogen determine the
preferred catalyst system
Olefins & diolefins determine need for catalyst size
and activity grading
Naphtha contaminants (i.e. Si and As) require
special metal trapping catalysts
18
Catalyst Selection
1000
100
10
do
e
B
Split
lys
a
t
a
fC
1
1
10
100
1,000
t i ma
p
O
t is
10,000
Hardware Considerations
Reactor design
downflow
multi-reactor, series or parallel
Vaporization
vapor phase reaction
never in radiant section of furnace
Virgin Naphtha
Cracked Naphtha
20 - 30
45 - 65
LHSV, h-1
3 - 10
1-5
Temperature, C
250 - 340
240 - 340
H2:Oil, Nm3/m3
50 - 100
250 500
7 - 10
15 - 45
ppH2, barg
21
Metals removal
Si and As are the major problems
Requires special metal trapping catalysts to remain activity
maintenance and to increase holding capacity and
22
23
24
IBP-75
75-126
126-149
149+
Cut yield
22%
30%
16%
32%
100%
S, ppm
75
100
200
600
250
N, ppm
20
75
35
Br. No.
100
75
45
25
70
Saturates
33
38
30
20
30
Olefins
65
50
30
20
45
Aromatics
12
40
60
25
RON
95
87
93
93
92
MON
81
77
81
81.5
80
Full Range
27
Purge
Compressor
Fuel Gas
Furnace
Olefin saturation
Guard
Reactor
HDS
Main
Reactor
Polishing
Trim
Reactor
HP Separator
LP Separator
Feed
Pump
28
Gasoline HDS
30
RON
MON
7-10
3-4
3-4
1-2
Hydrotreating + Isomerization
OCTGAIN (ExxonMobil)
ISAL (UOP/PDVSA)
Catalytic distillation
CDHDS+ (CDTech)
Selective adsorption
S-Zorb (Phillips)
31
SCANfining
Selective Naphtha HDS Technology
Low S feed
6
High S Feed
SCANfining I
High S feed
High S Feed
SCANfining II
Upgrading to SCANfining II
can control octane loss
30 - 40% incremental
investment
Full use of existing equipment
1
Low S Feed
SCANfining I
0
0
30
60
32
90
33
Catalyst Selection
A graded bed of active support material to saturate
the diolefins and prevent reactor pressure drop
problems
An active catalyst with high capacity for silica to
remove the silicon, sulfur, nitrogen, and olefins
Dilution of the coker naphtha with virgin and other
naphtha to reduce the reactor temperature rise to a
manageable level
35
Bed Grading
Recommended bed grading for coker naphtha units
HDN is Important
Nitrogen affects catalytic reformers
Affects the acidity of the noble metal CCR catalyst
Forms salts that deposit on compressors and exchangers
10
KF-841-1.3Q
KF-841-3Q
5
0
0
5
LHSV
39
10
Section of Reactor
40
10
Summary
Reformer performance dictates naphtha treating requirements
Virgin naphtha treating is usually a relatively simple process
Cracked naphtha treating is much more complicated
High exotherm
Contaminant removal
HDN is important
Hydrogen consumption
Reliance CNHT
MAIN
Recycle Gas
Feed
DIOS
TRIM
R1
R2
Product Recycle
R3
Hydrotreated
Naphtha
42
Reliance LNUU
Recycle Gas
Feed
DIOS
R3
MAIN 1
MAIN 2
R1
R2
Product Recycle
43
Petrochemical Naphtha
Hydrotreated
Product
Naphtha
S < 10 ppm, Br < 1
Low levels of Recombinant
Mercaptans can be allowed so
no trim reactor
DIOS Operation
45
Main RX Operation
Minimize product recycle to keep acceptable T in the first RX; typically 70C
Low product recycle increases ppH2 and lowers overall LHSV
Lowest possible product recycle is a function of the feed bromine number
RX1 product will act as heat sink in RX2
46
Trim RX Operation
Recombinant Mercaptans react very easily
Low operating temperature; typically 280C-300C
High LHSV; typically 10 h-1
Very low deactivation rates
47