Process Synthesis

Introduction
A relatively new ChE discipline the term

process synthesis was firstly defined by Rudd
(1968)
Lecture 1 Introduction to
Process Synthesis
First textbook Rudd, Power and Siirola (1973).

Process Synthesis. Prentice-Hall.
Definition (Westerberg, 1987): The discrete
decision-making activities of conjecturing:
1. Which of the many available component parts one
should use, and
2. How they should be interconnected to structure the
optimal solution to a given design problem?
Copyright@Dominic Foo
H84PSD - Process Synthesis & Design
Lecture 1 - 2
Main categories
Conventional approaches
Process synthesis can be broadly classified into 7

categories (Manousiouthakis & Allen, 1995):
Brainstorming among experienced engineers

Material synthesis
Reaction path synthesis
Reactor network synthesis
Separation network synthesis
Heat exchanger network synthesis (HENS H82PLD
Plant Design)
Mass exchanger network synthesis
Total flowsheet synthesis
Lecture 1 - 3
Evolutionary techniques: copy (or adapt) the last

design we or someone else did
Heuristics: based on experience-based rules
Lecture 1 - 4
Limitations of conventional approaches
A more formalised education?
Time and $$$ intensive
Systematic, fundamental, and generally applicable

techniques can be learned and applied to
synthesize optimal designs for improving process
performance.
Cannot enumerate the infinite alternatives

Is not guaranteed to come close to optimum
solutions (except for very simple cases or extreme
luck)
Does not shed light on global insights and key
characteristics of the process
This is possible via process synthesis, integration

& optimisation.
Severely limits groundbreaking & novel ideas.
Lecture 1 - 5
What is Process Synthesis?

Synthesis?
Process
input
(given)
Process
output
(given)
Concern with the activities in which the various process elements are
combined and the flowsheet of the system is generated. Hence, we know
process inputs and outputs and are required to revise the structure and
parameters of the flowsheet (for retrofitting design of an existing plant)
or create a new flowsheet (for grassroot design of a new plant).
Lecture 1 - 6
What is Process Analysis?

Analysis?
Process structure & parameter

(unknown)
Lecture 1 - 7
Process
input
(given)
Process
output
(unknown)
Process structure & parameter

(given)
Aimed at predicting how a synthesised process will perform. It involves the
decomposition of the process into its constituent elements (e.g. units) for individual
study of performance. Hence, once a process is synthesised, its detailed characteristics
(e.g. T, P, etc.) are predicted using analysis techniques, e.g. mathematical models &
computer-aided process simulation tools (e.g. HYSYS, Aspen Plus). Therefore, we are
given process inputs & flowsheet in process simulation to predict process outputs.
Lecture 1 - 8
In summary
Large problem
Decompose
Lar
ge
prob
Preliminary flowsheet
synthesis
lem
Integrate
(interactions)
(Seider et al., 2006, Ch 3)

Design
(Westerberg, 1987)
Process Design = Process Synthesis + Process Analysis

Lecture 1 - 9
Primitive problem statement

An opportunity has arisen to satisfy a new demand of 800 x
106 lb/yr vinyl chloride monomer (VCM), in a petrochemical
complex. Because VCM is an extremely toxic substance, it is
recommended that all new facilities be designed carefully to
satisfy governmental health and safety regulations.
(Example 1.3)
Vinyl chloride monomer:

H
Cl
C C
H
H
CHCl
1. Buy from competitor.

2. Buy Cl2 and react with in-house ethylene (C2H4).
3. Use surplus HCl and react with acetylene (or C2H4)
& O2 to produce 1,2-dichloroethane, which is
cracked to form VCM.
4. Design electrolysis plant to produce Cl2 & proceed
as in #2.
Polyvinyl chloride:
CHCl
Assessing the primitive statement

(alternatives)
CHCl
(Example 1.6)
CH2
CH2
CH2
Lecture 1 - 11
Lecture 1 - 12
Thermophysical property
database
Literature survey
Stanford Research Institute (SRI)
Design Reports a consortium
that produced a large number of
design reports on a various
processes.
Encyclopedias
Note: Be sure to read through the

complete citations in the text, before
you start a design project.
Perrys Handbook
Gmehling et al. (1980). Vapor-
Liquid Equilibrium Data

Collection
Handbooks
API Data Book
Reference Books
GPSA Data Book
Indexes (Applied Science & Tech

Index; Engineering Index; etc.)
Gallant (Physical Properties of
Patents
Simulators (but be sure to check
(Section 1.2)
Lecture 1 - 13
(Section 3.2)
Lecture 1 - 14
Chemical state
Environmental and safety data.

U. S. Environmental Protection Agency (EPA) website for Toxic
Chemical Release Inventory (TRI) containing >600 chemicals:
www.epa.gov/tri/chemical/index.htm.
Data for Process Design and Engineering Practice (Woods, 1995)
containing ratings of the National Fire Protection Association
(NFPA).
Perrys Chemical Engineers Handbook (Perry and Green, 1997).
Chemical Prices:
Chemical Market Reporter (biweekly newspaper)
Pay-site for Chemical Market Reporter:
http://www.chemicalmarketreporter.com
Website to locate articles on chemicals of commerce in trade
magazines at http://www.findarticles.com
http://ed.icheme.org/costchem.html
http://www.icis.com/StaticPages/a-e.htm
http://chemweek.com
(Section 3.2)
Hydrocarbons)
the data!)
Auxiliary Studies
Other data for process database
CRC Handbook
Lecture 1 - 15
Raw materials
(C2H4, Cl2)
Process
Flowsheet?
Desired product
(C2H3Cl)
Needed to define the state of each:

1) Mass (flowrate) from projected demand
2) Composition
3) Phase (solid, liquid, gas)
4) Form (particle size, etc.)
5) Temperature
6) Pressure
Lecture 1 - 16
Process operations
Synthesis steps
Most unit operations involve these basic operations:

1.
2.
3.
4.
5.
6.
7.
8.
Chemical reaction
Separation of chemicals
Phase separation
Change of temperature
Change of pressure
Change of phase
Mixing & splitting of streams
Solid operations (e.g. size enlargement/reduction)
2. Distribute the chemicals by matching
sources and sinks
between raw materials and the desired products. As new

unit is added to the process, effluent stream(s) are closer to
the required products.
(In/out/recycle)
3. Eliminate differences in composition
(Separations)
4. Eliminate differences in temperature,
(Heaters/coolers)
pressure, and phase
Each operation eliminate 1 or more property differences
1. Eliminate differences in molecular types (Reactors)
Lecture 1 - 17
5. Integrate tasks, i.e., combine operations
into unit operations

(Original source: Rudd et al., 1973)
Lecture 1 - 18
Step 1: Eliminate differences in

molecular types (define reactions)
Comparison with other approaches
Assemble potential reaction path information:
1. Batch versus continuous

2. Input-output structure
3. Recycle structure
Reactor
Vapor recovery system

Liquid recovery system
Solid recovery system
Heat exchange
network
Utilities
(Linnhoff et al., 1982;

Smith 1995, 2005)
5. Heat exchanger
network
C2H4 + Cl2 C2H3Cl + HCl
2. Hydrochlorination of acetylene
C2H2 + HCl C2H3Cl
4. Separation system
Separation &
recycle
1. Direct chlorination of ethylene
3. Thermal cracking of dichloroethane from chlorination of ethylene

C2H4 + Cl2 C2H4Cl2
C2H4Cl2 C2H3Cl + HCl
4. Thermal cracking of dichloroethane from oxychlorination of ethylene

C2H4 + 2HCl + O2 C2H4Cl2 + H2O
C2H4Cl2 C2H3Cl + HCl
5. Balanced process for chlorination of ethylene
(Douglas, 1988)
Lecture 1 - 19
C2H4 + Cl2 C2H4Cl2

C2H4 + 2HCl + O2 C2H4Cl2 + H2O
2C2H4Cl2 2C2H3Cl + 2HCl
Lecture 1 - 20

Chemical

Acetylene
Molecular
Weight
26.04
Chemical
Formula
C2H2
Chemical
Structure
H-C/C-H
Chlorine
70.91
Cl2
1,2 Dichloroethane
98.96
C2H4Cl2
Ethylene
28.05
C2H4
Hydrogen chloride
36.46
HCl
Vinyl chloride
62.50
C2H3Cl
Cl-Cl
Cl Cl
| |
H-C-C-H
| |
H H
H
H
\
/
C=C
/
\
H
H
H-Cl
H
Cl
\
/
C=C
/
\
H
H
Lecture 1 - 21
Locate price of all chemicals involved & determine gross profit (or
economic potential) of each reaction path, ignoring everything except
the chemicals themselves.
In Douglas (1988), economic potential is calculated for each level of
hierarchical decision.
Sources of chemical costs:
Chemical Marketing Reporter (a periodical)
Internet
Contact sales representatives of available companies
Example of chemical costs:
Chemical
Cost (cents/lb)
Ethylene
Acetylene
Chlorine
Vinyl chloride
Hydrogen chloride
Water
Oxygen (air)
18
50
11
22
18
0.05
0
Lecture 1 - 22


For each candidate set of reactions, determine the profit
Reaction path 1 is rejected based on low selectivity (not
(loss) of performing the reaction, based solely on the values

of the reactants & products.
Example profit calculation for path 3:
Gross profit for other paths are shown as follow:
Reaction path 3
Lb mole
Mole weight
Lb
Lb/lb VCM
cents/lb
C2H4
1
28.05
28.05
0.449
18
Cl2
1
70.91
70.91
1.134
11
C2H3Cl
1
62.50
62.50
1
22
HCl
1
36.46
36.46
0.583
18
So the gross profit is:

22(1) + 18(0.583) 18(0.449) 11(1.134) = 11.94 cents/lb VCM
Lecture 1 - 23
shown)
Gross profit
(cents/lb VCM)
Hydrochlorination of acetylene
-9.33*
Direct chlorination of ethylene
11.94
Thermal cracking of DCE from
3.42
oxychlorination of ethylene
Balanced process for
7.68
chlorination of ethylene
Path# Reaction path

2
3
4
5
* Note: acetylene is very expensive relative to ethylene

Lecture 1 - 24
Step 1: Eliminate differences in molecular

types (define reactions)
Overall production rate

Raw materials
(C2H4, Cl2)
Reaction path 3
Lb mole
Mole weight
Lb
Lb/lb VCM
cents/lb
Process
Flowsheet?
C2H4
1
28.05
28.05
0.449
18
Desired product
800 million lb/yr (330 days)
= 100,000 lb/hr
(C2H3Cl)
Cl2
1
70.91
70.91
1.134
11
C2H3Cl
1
62.50
62.50
1
22
HCl
1
36.46
36.46
0.583
18
If 100,000 lb/hr of VCM is produced, the other rates are calculated as:
C2H4: 44,900 lb/hr

Cl2: 113,400 lb/hr
HCl: 58,300 lb/hr
Lecture 1 - 25
Heat liberated
150 mmBTU/hr
Direct
Chlorination
90C, 1.5 atm
C2H4
44,900 lb/hr
Heat absorbed
52 mmBTU/hr
C2H4Cl2
158,300
lb/hr
Pyrolysis
500C
26 atm
Direct
Chlorination
HCl
58,300 lb/hr
HCl
C2H3Cl
C2H4Cl2
C2H3Cl
100,000 lb/hr
C2H4Cl2
C2H4
44,900 lb/hr
Involves the matching of sources & sinks of each chemicals

Assumption:
Dichloroethane
Sources (where chemical are found) & sinks

(where chemical are needed) of chemicals are not
shown yet, will depend on Step 2 distribution of
chemicals
Lecture 1 - 26
Effluent from direct chlorination needs no separation

Effluent from pyrolysis needs separation into pure products
Normal boiling points of chemicals involved:
HCl: -85C
C2H3Cl: -14C
C2H4Cl2 : 57C
Hence, distillation is possible option. The patent by B. F.
Goodrich recommended pressure setting for distillation:
Possible routes:
Lecture 1 - 27
A
A
B
C
C2H4 and Cl2 enter as in stoichiometric ratio of 1:1

By-product formation in direct chlorination (actual conversion =
98%) is neglected
C2H3Cl
100,000 lb/hr
Column 1: 12 atm
Column 2: 4.8 atm
105,500 lb/hr
Pyrolysis
Step 3: Eliminate composition

differences
Step 2: Distribution of chemicals

Cl2
113,400 lb/hr
HCl
58,300 lb/hr
Cl2
113,400 lb/hr
A
B
B
A
B
C
A
B
B
C
C
Lecture 1 - 28
Step 4: T, P & phase change

operations
Step 3: Eliminate composition

differences
One of the many possible options
The various ways of determining the best route are covered
in Synthesis of Separation Trains
Cl2
113,400
lb/hr
Cl2
113,400
lb/hr
150 mmBTU/hr
Direct
Chlorination
90C, 1.5 ATM
C2H4
44,900
lb/hr
C2H4Cl2
158,300
lb/hr
52 mmBTU/hr
115C
Pyrolysis
500C
26 atm
6C
C2H4
44,900
lb/hr
Distillation
Tower
4.8 ATM
-23.2C
33C
66 Hp
Direct
Chlorination
90C, 1.5 ATM
HCl
58,300 lb/hr
Distillation
Tower
12 ATM
150 mmBTU/hr
C2H4Cl2
Pressure
90C
1.5 atm Change
158,300
lb/hr
C2H3Cl
100,000 lb/hr
23 mmBTU/hr
21 mmBTU/hr
40 mmBTU/hr
Temp. 242C Phase 242C Temp.

112C
26 atm Change 26 atm Change 26 atm Change
BP Liq.
DP Vap.
52 mmBTU/hr
500C
26 atm
Pyrolysis
500C
26 atm
500C
26 atm
HCl
58,300 lb/hr
C2H3Cl
100,000 lb/hr
90C
Temp.
Change
170C
26 atm
Phase
Change
146C
93C
Temp.
Change
C2H4Cl2
6C
12 atm
BP Liq.
-23.2C
12 atm
33C
4.8 atm
146C
3.4 mmBTU/hr
105,500 lb/hr
93C
C2H4Cl2
105,500 lb/hr
Lecture 1 - 29
Step 5: Task integration
Lecture 1 - 30
The Synthesis Tree

The overall process of
synthesis can be seen by

the decision tree.
Path 1 & 2 cannot make
$$
Path 3 5 may make $$.
Lecture 1 - 31
Lecture 1 - 32
Introduction
Recalling the process operations in process synthesis:

Heuristics for process

synthesis
Chemical reaction (to eliminate differences in molecular type)

Mixing and recycle (to distribute the chemicals)
Separation (to eliminate differences in composition)
Temperature, pressure and phase change
Task integration (to combine tasks into unit operations)
This section deals with the heuristic rules that expedite the
(Seider et al., 2003, Ch 3)
selection and positioning of processing operations as

flowsheets are assembled.
These rules are based on experience and hold in general,
but should be tested (e.g., by simulation) to ensure that they
apply in the specific application.
Raw materials & chem reactions
Raw materials & chem reactions
Heuristic 1: Select raw materials and chemical

reactions to avoid, or reduce, the handling & storage
of hazardous and toxic chemicals.
Possible alternatives:
O
/\
C2H2 + O2
H2CCH2
(EG)
(EO)
O
OH OH
/\
| |
+ H2O
H2CCH2
H2CCH2
1. Use chlorine & caustic in a single reaction step to avoid

intermediate:
CH2=CH2 + Cl2 + 2NaOH (aq)
Example: Manufacture of Ethylene Glycol (EG) from Ethylene
Lecture 1 - 34
OH OH
| |
+ 2NaCl
H2CCH2
(R.3)
2. As EO is formed, react it with CO2 to form ethylenecarbonate, a much less active intermediate that can be
stored safely & hydrolyzed, to form the EG product as
needed:
(R.1)
(R.2)
O
/\
+ CO2
H2CCH2
Both reactions are highly exothermic, careful control needed.

Often designed with 2 reaction steps, with storage of the EO to enable
continuous production
O
|
C
/ \
CH2OOCH2
(R.4)
Danger: a water spill into an EO storage tank could lead to an accident
similar to the Bhopal incident.

Lecture 1 - 35
Lecture 1 - 36
Distribution of chemicals
Heuristic 2: Use excess reactant to completely consume

a valuable, toxic, or hazardous chemical reactant.
Heuristic 3: When nearly pure products are required,

the separations are easily accomplished, or
the catalyst is adversely affected by the inert
Example: Consider using excess ethylene in VCM production

Cl2
113,400 lb/hr
Heat liberated
150 mmBTU/hr
Direct
Chlorination
90C, 1.5 atm
Heat absorbed
52 mmBTU/hr
C2H4Cl2
C2H4
Pyrolysis
500C
26 atm
eliminate inert species before the reaction, when:
HCl
58,300 lb/hr
HCl
C2H3Cl
C2H4Cl2
Do not do this when a large exothermic heat of reaction
must be removed.
Example:
C2H3Cl
100,000 lb/hr
C2H4
44,900 lb/hr
C2H4Cl2
105,500 lb/hr
Lecture 1 - 37
Lecture 1 - 38
Purge streams
Heuristic 4: Introduce liquid / vapor purge streams to
Need to decide
whether to remove
inerts before
reaction...
provide exits for species that
enter the process as impurities in the feed

produced by irreversible side-reactions
when these species are in trace quantities and/or are

difficult to separate from the other chemicals.
Note: Purge flowrate selection depends on economics!
Example: NH3 synthesis loop
or after reaction?
The ease & cost of the separations must be assessed

accomplished by examining the physical properties upon
which the separations are based (via the use of simulation)
Lecture 1 - 39
Lecture 1 - 40
10
Purge streams
Selectivity
Heuristic 5: Do not purge valuable species or species that
Heuristic 7: For competing series or parallel

reactions, adjust the T, P, and catalyst to obtain
high yields of the desired products.
are toxic & hazardous, even in small concentrations.

Add separators to recover valuable species.
Add reactors to eliminate toxic and hazardous species.
In the initial distribution of chemicals, assume that

these conditions can be satisfied - obtain kinetics
data and check this assumption before developing
a base-case design.
Example: Catalytic converter in car exhaust system.
Lecture 1 - 41
Selectivity
Lecture 1 - 42
Selectivity
Example: Manufacture of allyl-chloride.
Kinetic data
Reaction
1
2
3
HR
(Btu/lbmole)
-4,800
-79,200
-91,800
ko
(lbmole.hr-1 ft-3atm-2)
206,000
11.7
4.6 x 108
E/R
(oR)
13,600
3,430
21,300
Lecture 1 - 43
What range of operating temp favors the production of

Allyl Chloride ?
Lecture 1 - 44
11
Reactive separation
Reactive separation
Example: MeOAc manufacture using reactive distillation
For reversible reactions, consider
conducting them in a separation device

capable of removing the products driving
the reactions to the right lead to very
different distributions of chemicals.
Example: Manufacture of Ethyl-acetate
MeOAc
HOAc
Reaction
zone
MeOH
Conventionally, this would call for reaction:

MeOH + HOAc MeOAc + H2O
H2O
followed by separation of products using a

sequence of separation towers.
Lecture 1 - 45
MeOH + HOAc MeOAc + H2O

Lecture 1 - 46
Separations
Separations
Heuristic 9: Separate liquid mixtures using

distillation and stripping towers, and liquid-liquid
extractors, among similar operations.
Heuristic 10: Attempt to condense vapor mixtures

with cooling water. Then, use Heuristic 9.
Select from partial
condensation, cryogenic
distillation, absorption,
adsorption, membrane
separation, etc.
(Douglas, 1988)
Attempt to cool
reactor products
using cooling water
Select from
distillation, enhanced
distillation, stripping
towers, liquid-liquid
extraction, etc.
(Douglas, 1988)
Lecture 1 - 47
Lecture 1 - 48
12
Separations
Heat transfer in reactors
Heuristic 11: Separate vapor mixtures using partial

condensers, cryogenic distillation, absorption towers,
adsorbers, and/or membrane devices.
Heuristic 21: To remove a highly-exothermic heat of reaction,

consider the use of excess reactant, an inert diluent, and cold
shots. These affect the distribution of chemicals and should be
inserted early in process synthesis.
Combination of
the previous 2
flowsheets
Lecture 1 - 49
Lecture 1 - 50
Heat transfer in reactors
Pumping and Compression
Heuristic 22: For less exothermic heats of reaction, circulate

reactor fluid to an external cooler, or use a jacketed vessel or
cooling coils. Also, consider the use of intercoolers.
Heuristic 43: To increase pressure of a stream, pump a liquid

rather than compress a gas; that is, condense a vapor, as long as
refrigeration (and compression) is not needed, before pumping.
Since work done by pumping
or compressions is given by:
Thus, it is almost always

preferable to condense a vapor,
pump it, and vaporize it, rather
than compress it.
Exception: if condensation
requires refrigeration.
Lecture 1 - 51
Lecture 1 - 52
13
Alternative 1
Example: Feed Preparation of Ethylbenzene

100,000 lb/h ethylbenzene is to be taken from
storage at 25 C & 1 atm and fed to a styrene
reactor at 400C & 5 atm.
Show two alternatives for positioning the
temperature and pressure-increase operations.
Lecture 1 - 53
Alternative 2
Lecture 1 - 54
Other sources of design heuristics
Additional references
Walas, S. M., Chemical Process Equipment Selection and
Douglas, J. M. (1988). Conceptual Design of Chemical Processes,

McGraw-Hill.
Linnhoff, B., Townsend, D. W., Boland, D., Hewitt, G. F., Thomas, B. E.
A., Guy, A. R., & Marshall, R. H. (1982). A User Guide on Process
Integration for the Efficient Use of Energy. Rugby: IChemE (heat exchanger
network synthesis).
Manousiouthakis, A. and Allen, D. (1995). Process Synthesis for Waste
Minimization. In: Biegler, L. T. and Doherty, M. F. Fourth International
Conference on Foundations of Computer-Aided Process Design. AIChE
Symposium Series. 91(304): 256-259. New York: AIChE.
Rudd, D. F. (1968). The Synthesis of System Designs, I. Elementary
Decomposition Theory. AIChE Journal, 14(2), 343-349.
Westerberg, A. W. (1987). Process Synthesis: A Morphology Review. In:
Liu, Y. A., McGee, H. A. and Epperly, W. R. ed. Recent Developments in
Chemical Process and Plant Design. New York: John Wiley and Sons.
Design, Butterworths, Stoneham, MA, 1988.

Turton, R., R. C. Bailie, W. B. Whiting, and J. A. Shaeiwitz,
Analysis, Synthesis, and Design of Chemical Processes,
Second Edition, Prentice- Hall, 2003 (Chapter 9 Utilizing
Experience-based Principles to Confirm the Suitability of a
Process Design.
Happel, J., and D. G. Jordan, Chemical Process Economics,
Second Edition, Marcel Dekker, New York, 1975
Appendix C.
Ulrich, G. D., A Guide to Chemical Engineering Process
Design and Economics, Wiley, 1984 Appendix B.
Lecture 1 - 55
Lecture 1 - 56
14

Process Synthesis

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Introduction

A relatively new ChE discipline the term

First textbook Rudd, Power and Siirola (1973).

H84PSD - Process Synthesis & Design