Lecture 2 PDF

Batch Process Modelling & Optimisation Intro to CAPD
PSE
LECTURE 2
Process Synthesis/Process
Creation
Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 1
Selection Criteria
PSE
Thermo-physical property data

physical properties (T, P, conversion)
Knovel
phase equilibria (VLE data) website,
Property prediction methods MSDS, NIST
Environmental and safety data chemical
webpage,
toxicity data patents, etc.
flammability data
Chemical Prices
e.g.
e g as published in the Chemical Marketing Reporter
Experiments
to check on crucial items above
Copyright @ CEPP, UTM SuperPro Designer

Preliminary Process Synthesis

PSE
Synthesis steps (Rudd, Powers, Sirrola, 1973) -

n Eliminate differences in molecular types
(
(chemical reaction))
o Distribute chemicals by matching sources and
sinks (mixing & recycle)
p Eliminate differences in composition
(separation)
q Eliminate differences in temperature,
temperature pressure
and phase
r Integrate tasks (combine tasks into unit
operations)
PSE
The Onion Model (Smith and Linnhoff, 1995)
Reactor
Separation &
Recycle System
Heat Exchanger
Network
Utilities

PSE
Synthesis Step 1:
Eliminate Differences in Molecular Types
Compare advantages and

disadvantages of all type of reactions
possible
RECALL
PSE
IRREVERSIBLE REVERSIBLE
Feed1 + Feed2 Product Feed1 + Feed2 Product + Byproduct
An excess of one feed component Maximum conversion is limited by the

would force another feed component equilibrium conversion
to complete conversion.
Which feed in excess ? To increase equilibrium conversion:

Cost Adding
g access of one feed
Safety Remove byproduct

PSE
WHAT IF SIDE REACTION IS REVERSIBLE?
Feed1 + Feed2 Product ...............(1)

Feed1 + Product Byproduct ...............(2)
TO MAXIMIZE SELECTIVITY,
INHIBIT THE BYPRODUCT FORMATION
By using excess of Feed2 will force Feed1 to
complete conversion and inhibit the side reaction
Or, removing the product as reaction proceed will force the

secondary reaction to left side and inhibit the Byproduct
formation
EXERCISE
PSE
Benzene is produced from Inlet Flow Outlet Flow

toluene, (kmol/hr) (kmol/hr)
H2 1858 1583
C6H5CH3 + H2 C6H6 + CH4 CH4 804 1083
C6H6 13 282
Biphenyl, the unwanted
C6H5CH3 372 93
byproduct is produced from
benzene, C12H10 0 4
2C6H6 C12H10 + H2
Calculate the conversion,

selectivity and yield with respect
to toluene.

PSE
H Cl
C=C
H H
Vinyl Chloride Manufacture
PSE REACTION PATH 1

C2H4 + Cl2 C2H3Cl + HCl (2.1)
n Direct chlorination of ethylene
Advantages:
Attractive solution.
Occurs spontaneously at a few hundred oC.
Disadvantages:
Low yield of VC.
Half
H lf off the
th expensive
i chlorine
hl i iis consumed
d tto produce
d
HCl by-product.

PSE REACTION PATH 2

C2H2 + HCl C2H3Cl (2.2)
o Hydrochlorination of acetylene
Advantages:
This exothermic reaction provides a good conversion
(98%) of C2H2 to VC in the presence of HgCl2 catalyst
impregnated in activated carbon at atmospheric
pressure.
These are fairly moderate reaction conditions, and
hence, this reaction deserves further study.
Disadvantages:
Flammability of C2H2
PSE
REACTION PATH 3
C2H4 + Cl2 C2H4Cl2 (2.3)
C2H4Cl2 C2H3Cl + HCl (2.4)
C2H4 + Cl2 C2H3Cl + HCl (2.1)
p Thermal cracking of C2H4Cl2 from chlorination of C2H4:
Advantages:
Conversion of ethylene to 1,2-dichloroethane in exothermic
reaction (2.3) is 98% at 90 oC and 1 atm with a Friedel-Crafts
catalyst such as FeCl3. This intermediate is converted to VC by
thermal cracking according to the endothermic reaction (2.4),
which occurs spontaneously at 500 oC with conversions as
high as 65%.
Disadvantage:
Half of the expensive chlorine is consumed to produce HCl
by-product.

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REACTION PATH 4
C2H4 + 2HCl + 21 O2 C2H4Cl2 + H2O (2.5)
C2H4 + HCl + 21 O2 C2H3Cl + H2O (2.6)
q Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
Advantages:
Highly exothermic reaction (2.5) achieves a 95% conversion
to C2H4Cl2 in the presence of CuCl2 catalyst, followed by
pyrolysis step (2.4) as Reaction Path 3.
Excellent
E ll t candidate
did t when
h costt off HCl is
i low.
l
Disadvantages:
Economics dependent on cost of HCl.
PSE REACTION PATH 5

C2H4 + Cl2 C2H4Cl2 (2.3)
C2H4 + 2HCl + 21 O2 C2H4Cl2 + H2O (2.5)
2C2H4Cl2 2C2H3Cl + 2HCl (2.4)
2C2H4 + Cl2 + 21O2 2C2H3Cl + H2O (2.7)
r Balanced Process for Chlorination of Ethylene:
Advantages:
Combination of Reaction Paths 3 and 4
All Cl2 converted to VC
No by-products!

PSE Chemicals participating in VC Manufacture:
Molecular Chemical Chemical

Chemical weight formula structure
Acetylene
y 26.04 C2H2 H-CC-H
Chlorine 70.91 Cl2 Cl-Cl

Cl Cl
| |
1,2- 98.96 C2H4Cl2 H-C-C-H
Dichloroethane | |
H H
H H
C=C
Ethylene 28 05
28.05 C2H4 H H
Hydrogen 36.46 HCl H-Cl

chloride
H Cl
C=C
Vinyl chloride 62.50 C2H3Cl H H
PSE Evaluation of Alternative Pathways
Reaction Path n is eliminated due its low selectivity.

This leaves four alternative paths, to be compared first
in terms of Gross Profit.
Profit
Chemical Bulk Prices
Chemical Cost (cents/lb)
Ethylene 18
Acetylene 50
Chlorine 11
Vi l chloride
Vinyl hl id 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0

PSE
Reaction path p C2H4 + Cl2 = C2H3Cl + HCl
lb-mole 1 1 1 1
Molecular weight 28.05 70.91 62.50 36.46
lb 28.05 70.91 62.50 36.46
lb/lb of vinyl chloride 0 449
0.449 1 134
1.134 1 0 583
0.583
cents/lb 18 11 22 18
Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC
Reaction Gross Profit

Overall Reaction
Path (cents/lb of VC)
o C2H2 + HCl = C2H3Cl -9.33
p C2H4 +Cl2 = C2H3Cl + HCl 11.94
q C2H4 + HCl + O2 = C2H3Cl + H2O 3.42
r 2C2H4 + Cl2 + O2 = 2C2H3Cl + H2O 7.68
EXERCISE
PSE
Monochlorodecane (MCD)
C10H21Cl is produced through,
C10H22 + C
Cl2 C10H21C
Cl +HCl
C
Molecular Price ($/kg)
A side reaction to which weight
unwanted byproduct HCl 36 0.35
dichlorodecane (DCD) is
Chlorine 71 0.21
produced
DEC 142 0.27
MCD 176 0.45
C10H22 + 2Cl2 C10H20Cl2 + 2HCl
DCD 211 0 00
0.00
Calculate E.P.
What would you suggest to
increase the production yield?

PSE Preliminary Flowsheet for Path p

Cl2 HCl
113,400 lb/hr 58,300 lb/hr
Raw Materials C2H4Cl2 Products
Direct Process Flowsheet? HCl
C2H4Chlorination
, Cl2 Pyrolysis
C2H3Cl, HCl
C2H3Cl
C2H4Cl2
C2H4 + Cl2 C2H4Cl2 C2H3Cl
C2H4 C2H4Cl2 C2H3Cl + HCl
100,000 lb/hr
44,900 lb/hr
Basis: 800 MM lb/year @ 330 days/year 100,000 lb/h VC

On this basis,
basis the HCl (sink) and reagent (sources) can be
computed (each flow is 1,600 lb-mol/h)
Next step involves distributing the chemicals by

matching sources and sinks.
PSE
Synthesis Step 2:
Matching sources and sinks
How much reactant do we need to obtain

the desired production rate? Can we
recycle un-reacted reactant?
C2H4 + Cl2 C2H4Cl2 (2.3)

(2 3)
C2H4 + Cl2 C2H3Cl + HCl (2.1)

PSE
NOTE: Assume a 100% conversion of the C2H4 in the chlorination reaction.
PSE
Only 60% of the C2H4Cl2 is converted to C2H3Cl with a

byproduct of HCl, according to Eqn. (2.4).
To satisfy the overall material balance, 158,300 lb/h of
C2H4Cl2 mustt produce
d 100,000
100 000 lb/h off C2H3Cl and
d 58,300
58 300
lb/h of HCl.
But a 60% conversion only produces 60,000 lb/h of VC.
The additional C2H4Cl2 needed is computed by mass
balance to equal:
[(1 - 0.6)/0.6] x 158,300 or 105,500 lb/h.
Its source is
It i a recycle
l stream
t f
from the
th separation
ti off C2H3Cl
from unreacted C2H4Cl2, from a mixing operation, inserted
to combine the two sources, to give a total 263,800 lb/h.

PSE
PSE
Synthesis Step 3:
Eliminate Differences in Composition
How to separate desired and undesired

product? Can we recycle to obtain
higher production?

PSE
The product of the chlorination reaction is nearly

pure C2H4Cl2, and requires no purification.
In contrast, the pyrolysis reactor conversion is
only 60%, and one or more separation operations
are required to match the required purities in the
C2H3Cl and HCl (sinks).
PSE

PSE
To eliminate differences in composition, 2 distillation towers

in series are inserted. Distillation is desirable because of
large volatility differences among the 3 species.
See the boiling points in table below.
Boiling point (oC) Critical constants
Chemical 1 atm 4.8 atm 12 atm 26 atm Tc,C Pc, atm

HCl -84.8 -51.7 -26.2 0 51.4 82.1
C2H3Cl -13
13.8
8 33 1
33.1 70 5
70.5 110 159 56
C2H4Cl2 83.7 146 193 242 250 50
PSE

PSE Synthesis Step 4:

Eliminate Differences in T, P and Phase
Identify all T,
T P and phase change to
determine the required utility
systems
PSE

PSE
How do we set the T and P?
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Guidelines for Process Operations
Sensible operating range to avoid severe processing difficulties
Parameter Range Rationale

Most equipment can go up to
Pressure Between 1 to 10 bar 10 bar without increase in
capital cost
Limited by utilities available:
Temperature 40 to 260C cooling water @ (30C) and
steam between 40 to 60 bar
(260C)

PSE
Pressure Range
The decision to operate outside the range of 1 to 10 bar usually is a
compromise between performance and the capital and operating costs
of process equipment.
Conditions Justification Penalty

In gas operations, increased
density, lower volume, smaller More costly, thicker-
P > 10 bar equipment (for the same walled equipment
residence time), higher quality needed
heating media (steam)
Larger equipment.
Prevent degradation
g of heat- Need special
P < 1 bar sensitive materials equipment
construction for
vacuum operations
PSE
Temperature Range
At elevated temperatures, common construction materials
(primarily carbon steel), suffer a significant drop in physical
strength and must be replaced by more costly materials.
Tensile Strength of Material

At Temperature Indicated (bar)
Temperature Ambient 400oC 550oC
Carbon Steel (grade 70) 1190 970 170
Stainless Steel (Type 302) 1290 1290 430
Carbon steel is unacceptable for temperatures above 400oC,

and that the use
se of stainless steel is severely
se erel limited.
limited
For higher service temperatures, more expensive alloys are
required and equipment may have to be refractory lined.
A decision to operate above 400C must be justified


Column Temperature
PSE
Tdew,C Tcw
Primarily dictated by cooling Tbub,C

water temp., Tcw :
TCW Tbub,C Tdew,C Tbub,R
Tdew,R TST
T dew,R
TST
T bub,R
PSE Synthesis Step 5:

Integrate Tasks
Complete the unit operations

operations

PSE
PSE

PSE
Development of Base-case Design
PSE
Process Equipment Identification
Consider P-101A/B:
P-101A/B identifies the equipment as a Pump
P-101A/B indicates that the pump is located in Area 100 of the plant
P-101A/B indicates that this specific pump is number 01 in Area 100
P-101A/B indicates that a back-up pump is installed. Thus, there are two identical pumps,
P-101A and P-101B. One pump will be operating while the other is idle.

PSE
Assembly of synthesis tree
Reaction Distribution Separations T, P and Task
path of chemicals phase integration
changes
n
o
EXERCISE B.P at 1 atm

PSE
Monochlorodecane (MCD) Molecular Boiling Pt.

C10H21Cl is produced through, weight (K)
HCl 36 188
C10H22 + C
Cl2 C10H21C
Cl +HCl
C Chlorine 71 239
DEC 142 447
A side reaction to which MCD 176 488
unwanted byproduct
DCD 211 495
dichlorodecane (DCD) is
produced
Assume:
C10H22 + 2Cl2 C10H20Cl2 + 2HCl
Incomplete conversion of both
feed.
Develop a process Reaction at 152 K, 2 atm.
flowsheet according the 5 Feed to the first separation is at
synthesis steps. 200K, 10 atm.

PSE
Group X
1 Acetone
2 Ammonia
3 Benzene
4 Acetic acid
5 Formaldehyde
6 Methanol
7 Phenol
8 Aniline
PSE
SUMMARY
Key information (materials and products)

Thermo-physical property data
Environmental and safety y data
Chemical Prices
Batch or continuous operations
Unit operations involved
Key steps in designing a process plant

Chemical reaction
Mixing & recycle
Separation processes
Eliminate differences in temperature, pressure and phase
Integrate tasks (combine tasks into unit operations)

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Batch Process Modelling & Optimisation Intro to CAPD

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 1

Thermo-physical property data

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 2

Copyright @ CEPP, UTM SuperPro Designer

Preliminary Process Synthesis

 Synthesis steps (Rudd, Powers, Sirrola, 1973) -

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 3

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 4

Copyright @ CEPP, UTM SuperPro Designer

Compare advantages and

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 5

Feed1 + Feed2 Product Feed1 + Feed2 Product + Byproduct

An excess of one feed component Maximum conversion is limited by the

Which feed in excess ? To increase equilibrium conversion:

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 6

Copyright @ CEPP, UTM SuperPro Designer

WHAT IF SIDE REACTION IS REVERSIBLE?

Feed1 + Feed2 Product ...............(1)

Or, removing the product as reaction proceed will force the

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 7

Benzene is produced from Inlet Flow Outlet Flow

Calculate the conversion,

Copyright @ CEPP, UTM SuperPro Designer

Vinyl Chloride Manufacture

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 9

PSE REACTION PATH 1

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Copyright @ CEPP, UTM SuperPro Designer

PSE REACTION PATH 2

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PSE REACTION PATH 5

r Balanced Process for Chlorination of Ethylene:

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 14

Copyright @ CEPP, UTM SuperPro Designer

PSE Chemicals participating in VC Manufacture:

Molecular Chemical Chemical

Chlorine 70.91 Cl2 Cl-Cl

Hydrogen 36.46 HCl H-Cl

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 15

PSE Evaluation of Alternative Pathways

Reaction Path n is eliminated due its low selectivity.

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Copyright @ CEPP, UTM SuperPro Designer

Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC

Reaction Gross Profit

p C2H4 +Cl2 = C2H3Cl + HCl 11.94

q C2H4 + HCl + O2 = C2H3Cl + H2O 3.42

r 2C2H4 + Cl2 + O2 = 2C2H3Cl + H2O 7.68

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Copyright @ CEPP, UTM SuperPro Designer

PSE Preliminary Flowsheet for Path p

Basis: 800 MM lb/year @ 330 days/year 100,000 lb/h VC

Next step involves distributing the chemicals by

How much reactant do we need to obtain

C2H4 + Cl2 C2H4Cl2 (2.3)

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Copyright @ CEPP, UTM SuperPro Designer

NOTE: Assume a 100% conversion of the C2H4 in the chlorination reaction.

Copyright@FKKKSA, UTM Computer-Aided Process Simulation Project Intro to PD - 21

Only 60% of the C2H4Cl2 is converted to C2H3Cl with a

Synthesis steps (Rudd, Powers, Sirrola, 1973) -