Kwame Nkrumah University of

Science & Technology (KNUST), Kumasi, Ghana

CHE 451: CHEMICAL PROCESS DESIGN & ECONOMICS

Unit 2a Introduction to Process Synthesis

Dr. Augustine Ntiamoah

Department of Chemical Engineering
Introduction to Process Synthesis
Introduction to process synthesis, process synthesis
models, economic potential, use of heuristics in process
synthesis
Process Synthesis

▪ For given desired products and available raw materials, process

synthesis is concerned with the selection and arrangement of
process stages, and selection of equipment and processes required
to perform the function of each stage in order to obtain the products
from the raw materials, while satisfying a predetermined objective
such as minimum cost.

Chemical Process Design & Economics KNUST- Ghana 3

Components of Chemical Processes

▪ Each block represents a stage in the overall process for producing a

product from raw materials.
▪ Each stage is a collection of equipment and/or processes required to
accomplish a defined task. For example, product separation section
may contain (four distillation columns and two flash units).

Chemical Process Design & Economics KNUST- Ghana 4

Guidelines for Process Synthesis

▪ There are guidelines for process synthesis but there are no general
methods that explicitly “output” the best process.
▪ Instead, process synthesis is a trial-and-error activity: A reasonable
process alternative is put together, analysed to some depth, and then
possibly abandoned in favour of a second or third alternative.
▪ Two important process synthesis models/guidelines are the “onion”
model and the hierarchical approach by Douglas.

Chemical Process Design & Economics KNUST- Ghana 5

Guidelines for Process Synthesis

(i) The onion model of process synthesis

• The reactor/separation/recycle structure
defines the essential process flowsheet
architecture, namely the chemical reactor
interacting with separators through recycles.
• Heat exchanger network- process integration
for optimal use of heat (heat recovery).
• Utility systems design to provide additional
heating and cooling requirements that cannot
be satisfied through heat recovery.

Chemical Process Design & Economics KNUST- Ghana 6

Guidelines for Process Synthesis

(ii) Hierarchical approach to process synthesis

▪ Level 1: Batch vs. Continuous.
▪ Level 2: Input-output structure of the flowsheet
▪ Level 3: Recycle structure of the flowsheet
▪ Level 4: Structure of separation system
▪ Level 5: Heat recovery

Chemical Process Design & Economics KNUST- Ghana 7

▪ Process synthesis by hierarchical approach will be discussed
through a case-study: synthesis of benzene via hydrodealkylation
(HDA) of toluene.
▪ Read the following article/paper by Douglas, and write up a summary
on each of the five decision levels of hierarchy involved in process
synthesis:
▪ Douglas, J.M. (1985), A hierarchical decision procedure for process
synthesis. AIChE Journal. volume 31, issue 3. pg. 353-362.

Chemical Process Design & Economics KNUST- Ghana 8

The onion model of process synthesis

Layer 1: The Reactor

▪ The reactor is the heart of the chemical process. This is where raw
materials are converted into products.
▪ Factors to consider when synthesising reactor system:
– The right reactor model (CSTR, plug-flow reactor.)
– Operating conditions (isothermal, adiabatic, vacuum, etc)
– Reaction equilibrium and kinetics
– How should the product conversion and yield be determined?
– Is catalyst needed?

Chemical Process Design & Economics KNUST- Ghana 9

The onion model of process synthesis
Layer 2: Separation and Recycle Structure
▪ Products and by-products formed in the reactor need to be separated from
unconverted reactant for further purification, while unconverted raw
materials are recycled back to the reactor.
▪ Separation systems can be broadly classified as liquid or vapour
separations.
– Vapour separation systems include condensers, flash tanks, absorbers,
adsorbers, and gas separation membranes. These unit operations are
normally used to purify a vapour recycle stream before it re-enters the
process.
– Liquid separation systems include distillation, solvent extraction,
centrifugation, etc.
– Selection of separation processes will be discussed.

Chemical Process Design & Economics KNUST- Ghana 10

The onion model of process synthesis

Layer 2: Separation and Recycle Structure cont’d

▪ Raw materials can make up from 25 to 75% of total operating costs.
Hence, it is important to recover as much raw material as possible.
– Exception is when raw materials are very cheap (e.g, air, H2O)

▪ The purpose of a recycle stream is to take unreacted reactants and

reuse them, ensuring the highest process efficiency possible.
▪ Beware of the accumulation of unwanted pollutants in the process
loop, and purge as required.

Chemical Process Design & Economics KNUST- Ghana 11

The onion model of process synthesis

Layer 3: Heat Exchange Network

▪ The need for heat exchanges is considered. Heat exchange network
(HEN) is optimized and integrated by pinch analysis based on first &
second laws of thermodynamics
– Minimum number of heat exchangers
– Minimum utility requirements
– Identification of hot and cold streams
– Identification of pinch temperature

Chemical Process Design & Economics KNUST- Ghana 12

The onion model of process synthesis

Layer 4: Utilities
▪ Utility system design involves selection of hot and cold utilities (using
process integration tools)
▪ Other options to be explored include the placement of heat pump
and heat engine.
▪ A process simulator is a useful tool to evaluate the selected utilities.

Chemical Process Design & Economics KNUST- Ghana 13

Economic Potential- Selection of Reaction
Pathways

Chemical Process Design & Economics KNUST- Ghana 14

Economic Potential

▪ Given that the objective is to manufacture a certain product, there

are often a number of alternative reaction paths to that product.
▪ Reaction paths that use the cheapest raw materials and produce the
smallest quantities of by-products are to be preferred.
▪ A simple economic criterion in selecting reaction pathways is the
Economic Potential, EP.
▪ EP = Value of products – Cost of raw materials
▪ Choose process with large economic potential to investigate further.
If EP < 0, then don’t bother to pursue this process.

Chemical Process Design & Economics KNUST- Ghana 15

Economic Potential

Example 1
▪ Consider the need to manufacture vinyl chloride, a monomer
intermediate for the production of polyvinyl chloride (PVC)

▪ There are at least four reaction paths that can be readily exploited.

Chemical Process Design & Economics KNUST- Ghana 16

Possible Reactions for vinyl chloride

▪ Reaction path 1: Hydrochlorination of acetylene

▪ Reaction path 2: Thermal cracking of dichloroethane (C2H4Cl2) from

chlorination of ethylene (C2H4):

Chemical Process Design & Economics KNUST- Ghana 17

▪ Reaction path 3: Thermal cracking of C2H4Cl2 from Oxychlorination
of ethylene:

Chemical Process Design & Economics KNUST- Ghana 18

▪ Reaction path 4: Combination of reaction Paths 2 and 3.

Chemical Process Design & Economics KNUST- Ghana 19

Economic data:

Mwt Chemical Value

Chemical
(kg/kgmol) formula ($/kg)
Acetylene 26 C2H2 1.00
Chlorine 71 Cl2 0.23
Ethylene 28 C2H4 0.58
Hydrogen chloride 36 HCl 0.39
Vinyl chloride 62 C2H3Cl 0.46

Chemical Process Design & Economics KNUST- Ghana 20

Economic Potential

▪ Let’s take reaction path 2 as an example for detailed calculation of

economic potential
Reaction path 2 C2H4 + Cl2 = C2H3Cl + HCl
kgmol 1 1 1 1
MWt 28 71 62 36
kg 28 71 62 36
kg/kg of VC 0.452 1.145 1 0.581
$/kg 0.58 0.23 0.46 0.39
▪ EP = 0.46(1) + 0.39(0.581) – 0.58(0.452) – 0.23(1.145) = 0.16 $/kg VC

Chemical Process Design & Economics KNUST- Ghana 21

Economic Potential Summary

▪ Using similar procedures, economic potential for all reaction paths

can be calculated as follows:
Reaction Overall Economic Potential
Path Reaction ($/kg of VC)
1 C2H2 + HCl = C2H3Cl -0.19

2 C2H4 + Cl2 = C2H3Cl + HCl 0.16

3 C2H4 + HCl + ½ O2 = C2H3Cl + H2O -0.25

4 2C2H4 + Cl2 + ½ O2 = 2C2H3Cl + H2O 0.07

Chemical Process Design & Economics KNUST- Ghana 22

▪ Paths 1 and 3 are clearly not viable.
▪ Path 2 shows a positive economic potential when the by-product HCl
can be sold. If it cannot be sold, then EP = -0.07 $/kg VC.
▪ In general, projects should not be justified on the basis of the by-
product value.
▪ In the industry, vinyl chloride is produced by reaction path 4.

Chemical Process Design & Economics KNUST- Ghana 23

Example 2: Production of Monochlorodecane
Path 1: 5C10H22 + 6 Cl2 → 4C10H21Cl + 6HCl + C10H20 + Cl2
Path 2: C10H20 + HCl → C10H21Cl
Path 3: C10H21OH + HCl → C10H21Cl + H2O
▪ Which reaction path has more economic potential?

Chemical Process Design & Economics KNUST- Ghana 24

▪ Economic values

Chemical Chemical Value

formula ($/Ibmol)
Decane C10H22 4.80
Decene C10H20 12.00
Decanol C10H21OH 14.00
Chlorine Cl2 1.77
Hydrochloric acid HCl 1.00
MCD C10H21Cl 16.00

Chemical Process Design & Economics KNUST- Ghana 25

▪ EP for reaction path 1 = = $8.845/lbmol MCD
▪ EP for reaction path 2 = = $3.00/lbmol MCD
▪ EP for reaction path 3 = = $1.00/lbmol MCD
▪ Ranking of EP: Path 1 > Path 2> Path 3

Chemical Process Design & Economics KNUST- Ghana 26

Example 3: Production of Benzene
▪ There are generally two routes to the production of benzene:
▪ Reaction path 1: Hydrodealkylation of toluene (HDA)
C6H5CH3 + H2  C6H6 + CH4
Toluene Benzene

▪ Reaction path 2: Direct disproportionation of toluene

C6H5CH3  C6H6 + C6H4(CH2)2
Toluene Xyene

▪ Evaluate the economic potential of each reaction route.

Chemical Process Design & Economics KNUST- Ghana 27

▪ The following prices for raw materials & products costs are given:

Chemical Value ($/kg)

Benzene 0.919
Toluene 1.033
Methane 0.302
Hydrogen 1.00
Mixed xylenes 0.820

Chemical Process Design & Economics KNUST- Ghana 28

▪ EP (reaction path 1)
▪ Value of raw materials (use 1 kmol of toluene feed as a basis)
92 kg of Toluene = ( 92 kg)($ 1.033/ kg) = $ 95.04
2kg of Hydrogen = ( 2 kg)($ 1.000/ kg) = $ 2.00
▪ Value of Products
Benzene = ( 78 kg)($ 0.919/ kg) = $ 71.68
Methane = ( 16 kg)($ 0.302/ kg) = $ 4.83
▪ EP = (71.68 + 4.83) – (95.04 + .00)= –$ 20.53 (–$ 0.223/ kg toluene)

Chemical Process Design & Economics KNUST- Ghana 29

▪ EP (reaction path 1) = –$ 0.223/ kg toluene
▪ EP (reaction path 2) = –$0.171/kg toluene
▪ Benzene via disproportionation of toluene is unprofitable but better
than by HDA process
▪ Toluene disproportionation is currently the preferred process for
benzene production.

Chemical Process Design & Economics KNUST- Ghana 30