Process Synthesis
Prof. Shantha Amarasinghe
July 28, 2025
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Process synthesis is the step in design where the chemical engineer selects the
component parts and how to interconnect them to create his flowsheet.
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What are the skills expecting to develop ?
Manufacture of Vinyl chloride
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Difference
Process analysis ? Process design
In process Analysis you start with an available PFD In process design you synthesize the process and
develop the PFD
Block Flow Diagram
• Group of connected blocks of process
units
• Lines with arrows connect blocks and
represent process streams
• Raw materials enter on the left
• Products exit on the right
• 4 kinds of “process” units:
Mixers
Reactors
Splitters
Separators
butter
C12H22O11
flour
Raw chocolate chip
eggs Cookie dough
Mixer
NaCl
NaHCO3
Chocolate chips
Raw chocolate chip Baked chocolate chip
Cookie dough Cookies
Reactor (Oven)
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4 dozen cookies 3 dozen cookies
75% choc chip 75% choc chip
25% peanut butter 25% peanut butter
Splitter
1 dozen cookies
75% choc chip
25% peanut butter
4 dozen cookies 3 dozen cookies
75% choc chip 97.5% choc chip
25% peanut butter 2.5% peanut butter
Separator
1 dozen cookies
8.3% choc chip
91.7% peanut butter
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Onion ring model
The onion ring model, in the context of
process synthesis, refers to a
hierarchical approach where the
process is broken down into concentric
layers, similar to an onion, with each
layer representing a different level of
detail or dependency. It's a visual tool
for understanding and analyzing
complex processes by revealing Hierarchical Targeting of Hydrogen Network System and
interdependencies between different Heat Integration in a Refinery
components or stages
Process design starts with the reactor.
Why?
The reactor design dictates the separation and recycle problem.
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Waste ?
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A mixture of hydrogen and nitrogen is fed to a catalytic reactor where some of the hydrogen
and nitrogen is converted to ammonia. The reactor effluent is sent to a condenser where all of
the ammonia is condensed. The condensed ammonia is sent to product storage. The
uncondensed hydrogen and nitrogen are recycled by being mixed with a fresh feed of
the same composition. The resulting mixture is fed to the reactor.
purge
recycle ?
N2, H2
“feed” ?
N2 reactor condenser
H2 “effluent”
NH3
NH3
N2
liquid
H2
Storage
tank
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Your role in the chemical process
1. Specification of equipment, and materials and their subsequent arrangement
into processes which control the environment of a chemical or physical
operation to achieve a desired output.
2. The analysis of the operation of existing chemical or physical processes in
order to alter the processing operation to achieve a desired result.
Process design vs. Process analysis
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Both problems require analysis and design functions.
Example:
An oil fired boiler in an oil refinery is not producing the required amount of steam.
The chemical engineer first analyses the boiler to determine the nature of the
problem (like a diagnosis, this is the analysis).
Then the engineer proposes a solution which may involve some design. So, for
example, If the poor performance was caused by inadequate supply of air for
combustion, the engineer would determine the correct amount of air, and to supply
the amount of air s/he might have to design (or specify) a new air blower.
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Manufacturing of Vinyl Chloride Monomer
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Hierarchy of Process Design
Before discussing the steps involved in the conceptual design of a process, it should be noted that
often the most important decision in the evolution of a process is the choice of which chemical
syntheses or routes should be investigated to produce a desired product. The identification of
alternative process chemistries should be done at the very beginning of any conceptual design. The
conceptual design and subsequent optimization of a process are “necessary conditions” for any
successful new process. However, the greatest improvements (savings) associated with chemical
processes are most often due to changes, sometimes radical changes, to the chemical pathway used
to produce the product. Most often, there are at least two viable ways to produce a given chemical.
These alternative routes may require different raw materials and may produce different byproducts.
The cost of the raw materials, the value of the by-products, the complexity of the synthesis, and the
environmental impact of any waste materials and pollutants produced must be taken into account
when evaluating alternative synthesis routes. 17
Example: Vinyl Chloride Manufacture
1 Direct chlorination of ethylene: C2H4 + Cl2 → C2H3Cl + HCl
2 Hydrochlorination of acetylene: C2H2 + HCl → C2H3Cl
3 Thermal cracking of C2H4Cl2 from chlorination of C2H4: C2H4 + Cl2 → C2H4Cl2 Selected
C2H4Cl2 → C2H3Cl + HCl
C2H4 + Cl2 → C2H3Cl + HCl
4 Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
5 Balanced Process for Chlorination of Ethylene:
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Assembly of synthesis tree
Expected outcome
Algorithmic methods are very effective for the synthesis,
analysis and optimization of alternative flowsheets.
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Synthesis steps
1 Identify the input/output structure of the process Reaction path
2 Identify and define the recycle structure of the Distribution of chemicals
process
3 Identify and design the general structure of the Separations
separation system
4 Identify and design the structure of utility T, P and Phase change
requirement
5 Combine tasks into unit operations Integrate tasks
Clearly show these five steps in your report
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Step 1
Identify the input/output structure of the process – Reaction path
Thermal cracking of C2H4Cl2 from chlorination of C2H4
Conversion
Assumed ?
C2H4 + Cl2 → C2H4Cl2 100% 800 MM lb/year @ 330 days/y 100,000 lb/hr VC
C2H4Cl2 → C2H3Cl + HCl 60%
------------------------------
C2H4 + Cl2 → C2H3Cl + HCl
??????? ??????
???????
Decide whether the process will be batch or continuous? 22
Batch or continuous Process ?
Some Factors to Consider When Deciding between Batch and Continuous Processes
Considering the scale of operation continuous process is selected
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Preliminary Flowsheet for the selected Path
? ?
?????
113600 ????
58400
158400 lb/hr
?
?????
44800
800 million lb/year @ 330 days/y 100,000 lb/h of VC
C2H4Cl2 → C2H3Cl + HCl
Molecular weight 99 62.5 36.5
Moles/h 1600 1600 1600
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Now include all the necessary information of the reactions
Required
158400 lb/hr
58400
113600 …
44800
A conversion of 100% is assumed
* Overall material balance without recycle - important
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Reactor pressure levels:
– Chlorination reaction: 1.5 atm is recommended, to eliminate the possibility
of an air leak into the reactor containing ethylene.
– Pyrolysis reaction: 26 atm is recommended by the B.F. Goodrich patent
(1963) without any justification. Since the reaction is irreversible, the
elevated pressure does not adversely affect the conversion. Most likely,
the patent recommends this pressure to reduce the size of the pyrolysis
furnace, although the tube walls must be considerably thicker and many
precautions are necessary for operation at elevated pressures.
– The pressure level is also an important consideration in selecting the
separation operations, as will be discussed in the next synthesis step.
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Step 2
Identify and define the recycle structure of the process - Distribution of chemicals
The effluent stream from the pyrolysis operation is the source for the C2H3Cl
product, the HCl by-product, and the C2H4Cl2 recycle.
???
100 % Conversion 60 % Conversion
???
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• Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct of HCl, according to Eqn.
(2.4).
C2H4Cl2 → C2H3Cl + HCl
• To satisfy the overall material balance, 158,300 lb/h of C2H4Cl must produce 100,000 lb/h of
C2H3Cl and 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 a recycle stream from the separation of C2H3Cl from unreacted C2H4Cl2, from a
mixing operation, inserted to combine the two sources, to give a total 263,800 lb/h.
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(158000 + x) 60%=(100000+58400)
113600 lb/hr 158400 lb/hr + x ? 58400 lb/hr
C2H4Cl2
44800 lb/hr 100% 60%
• Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct of HCl, according to Eqn. (2.4).
C2H4Cl2 → C2H3Cl + HCl (2.4)
• To satisfy the overall material balance, 158,400 lb/h of C2H4Cl must produce 100,000 lb/h of
C2H3Cl and 58,400 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 158,400 or 105,600 lb/h.
• Its source is a recycle stream from the separation of C2H3Cl from unreacted C2H4Cl2, from a
mixing operation, inserted to combine the two sources, to give a total 264,000 lb/h.
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The effluent stream from the pyrolysis operation is the source for the C2H3Cl
product, the HCl by-product, and the C2H4Cl2 recycle.
What are the other
process units ?
105600 lb/hr 58400 lb/hr
113600 lb/hr
158400
lb/hr
44800 lb/hr
105600 lb/hr
* Overall material balance with recycle - important
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Step 3
Identify and design the general structure of the separation system - Separations
• 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.
• One possible arrangement is given in the next slide. The data below explains the design
decisions made.
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* Overall material balance with
recycle and separation - important
There may be other, possibly better alternative configurations
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Step 4
Identify and design the structure of utility requirement - T, P and Phase change
Now think what to change T, P and Phase
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Step 5
Combine tasks into unit operations – Integrate tasks
Now think how to change T, P and Phase
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Identify the required utility units to get T, P and Phase change
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Development of Base-case Design
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Assembly of synthesis tree
Algorithmic methods are very effective for the synthesis, analysis and optimization
of alternative flowsheets.
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Better to give a Table indicating the function, operating conditions of each unit
What if the reaction is biological ?
Biochemical reactor
Any difference to our analysis ?
1 Identify the input/output structure of the process Reaction path
2 Identify and define the recycle structure of the process Distribution of chemicals
3 Identify and design the general structure of the separation system Separations
4 Identify and design the structure of utility requirement T, P and Phase change
5 Combine tasks into unit operations Integrate tasks
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Thank you !