LECTURE 05 PRODUCT and PROCESS DESIGN

WORKSHOP on
PRODUCT AND PROCESS DESIGN

LECTURE 05: HEURISTICS FOR PROCESS

SYNTHESIS

Daniel R. Lewin
Department of Chemical Engineering
Technion, Haifa, Israel
Ref: Seider, Seader and Lewin (2004), Chapter 5

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Introduction
Recalling the process operations in 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 lecture deals with the heuristic rules that expedite
the 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.
Later, in Part 2, we will see how algorithmic methods are
used to improve on design decisions.

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Instructional Objectives
When you have finished studying this unit, you should:
Understand the importance of selecting reaction paths that do
not involve toxic or hazardous chemicals, and when unavoidable, to
reduce their presence by shortening residence times in the
process units and avoiding their storage in large quantities.
Be able to distribute the chemicals in a process flowsheet, to
account for the presence of inert species, to purge species that
would otherwise build up to unacceptable concentrations, to
achieve a high selectivity to the desired products.
Be able to apply heuristics in selecting separation processes to
separate liquids, vapors, and vapor-liquid mixtures.
Be able to distribute the chemicals, by using excess reactants,
inert diluents, and cold shots, to remove the exothermic heats of
reaction.
Understand the advantages of pumping a liquid rather than
compressing a vapor.

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Raw Materials and Chemical Reactions

Heuristic 1: Select raw materials and chemical reactions to

avoid, or reduce, the handling and storage of
hazardous and toxic chemicals.
Example: Manufacture of Ethylene Glycol (EG).
O
1
C2H4 + -2 O2 → CH2 - CH2 (R.1)
O OH OH
CH2 - CH2 + H2O → CH2 - CH2 (R.2)
Since both reactions are highly exothermic, they need to be
controlled carefully. But a water spill into an ethylene-oxide storage
tank could lead to an accident similar to the Bhopal incident. Often
such processes are designed with two reaction steps, with storage of
the intermediate, to enable continuous production, even when
maintenance problems shut down the first reaction operation.

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Alternatives to the two-step EG process

Use chlorine and caustic in a single reaction step, to avoid

the intermediate:
OH OH
CH2=CH2 + Cl2 + 2NaOH(aq) → CH2CH2 + 2NaCl (R.3)

As ethylene-oxide is formed, react it with carbon dioxide

to form ethylene-carbonate, a much less active
intermediate that can be stored safely and hydrolyzed,
to form the ethylene-glycol product, as needed:
O
O C
CH2 - CH2 + CO2 → O O (R.4)
CH2 CH2

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Distribution of Chemicals

Heuristic 2: Use an excess of one chemical reactant in a

reaction operation to completely consume a
second valuable, toxic, or hazardous chemical
reactant.
Example: Consider using excess ethylene in DCE production

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Distribution of Chemicals (Cont’d)

Heuristic 3: When nearly pure products are required,
eliminate inert species before the reaction
operations, when the separations are easily
accomplished, or when the catalyst is
adversely affected by the inert
Do not do this when a large exothermic
heat of reaction must be removed.
Example:

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Distribution of Chemicals (Cont’d)

Need to decide whether to
remove inerts before
reaction...

… or after reaction...

Clearly, the ease and cost of the separations must be assessed.

This can be accomplished by examining the physical properties upon
which the separations are based, and implies the use of simulation

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Distribution of Chemicals (Cont’d)

Heuristic 4: Introduce liquid or vapor purge streams to
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.
Example: NH3 Synthesis Loop.

Note: Purge flow rate selection depends on economics!

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Distribution of Chemicals (Cont’d)

Heuristic 5: Do not purge valuable species or species that
are toxic and hazardous, even in small
concentrations.
– Add separators to recover valuable species.
– Add reactors to eliminate toxic and hazardous
species.
Example: Catalytic converter in car exhaust system.

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Distribution of Chemicals (Cont’d)

Heuristic 7: For competing series or parallel reactions,
adjust the temperature, pressure, and catalyst
to obtain high yields of the desired products.
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: Manufacture of allyl-chloride.

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Allyl Chloride Manufacture (Cont’d)

Example: Manufacture of allyl-chloride.

Kinetic data
∆HR ko
Reaction E/R (oR)
Btu/lbmole lbmole/(hr ft3atm2)
1 -4,800 206,000 13,600
2 -79,200 11.7 3,430
3 -91,800 4.6 x 108 21,300

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Allyl Chloride Manufacture (Cont’d)

9.60E-04

9.70E-04

9.80E-04

9.90E-04

1.00E-03

1.02E-03
1.01E-03
-0.4

-0.8
ln(k)

-1.2

ln(k1)
-1.6 ln(k2)
1/T (980<T<1042 deg R) ln(k3)

What range of operating temperatures favor

production of Allyl Chloride ?

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Distribution of Chemicals (Cont’d)

Heuristic 8: For reversible reactions, especially, consider

conducting them in a separation device capable
of removing the products, and hence, driving
the reactions to the right. Such reaction-
separation operations lead to very different
distributions of chemicals.
Example: Manufacture of Ethyl-acetate using reactive
distillation.
Conventionally, this would call for reaction:
MeOH + HOAc ← MeOAc + H2O,
→

followed by separation of products using a

sequence of separation towers.

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MeOAc Manufacture using Reactive Distillation

MeOAc

HOAc
Reaction
zone
MeOH

H 2O
→
MeOH + HOAc ← MeOAc + H2O

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Separations

Heuristic 9: Separate liquid mixtures using distillation and

stripping towers, and liquid-liquid extractors,
among similar operations.
Ref: Douglas (1988)

Select from
distillation, enhanced
distillation, stripping
towers, liquid-liquid
extraction, etc.

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Separations (Cont’d)

Heuristic 10: Attempt to condense vapor mixtures with

cooling water. Then, use Heuristic 9.

Ref: Douglas (1988) Select from partial

condensation,
cryogenic distillation,
absorption, adsorption,
membrane separation,
etc.

Select from
distillation, enhanced
distillation, stripping
towers, liquid-liquid
extraction, etc.
Attempt to cool
reactor products
using cooling water

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Separations (Cont’d)

Heuristic 11: Separate vapor mixtures using partial

condensers, cryogenic distillation, absorption
towers, adsorbers, and/or membrane devices.
Ref: Douglas (1988)

Combination of the
previous two flowsheets

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Heat Transfer in Reactors

Although heat transfer in reactors is better discussed in the
context of heat and power integration (see Lectures 6- 8), it
is treated here because many methods dealing with heat
transfer in reactors also affect the distribution of chemicals.
Treated first are exothermic reactors.

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.
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.

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Heat Transfer in Reactors (Cont’d)

Heuristic 21: To remove a highly-exothermic heat of
reaction, consider the use of…

excess reactant

an inert diluent

cold shots.

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Heat Transfer in Reactors (Cont’d)

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.

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Heat Transfer in Reactors (Cont’d)

Example: TVA design for NH3 synthesis converters

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Heat Transfer in Reactors (Cont’d)

Example: NH3 synthesis converter cold-shot optimization

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Heat Transfer in Reactors (Cont’d)

Example: NH3 synthesis converter cold-shot optimization

Before [0.100, 0.240]

After optimization – φφ = [0.277, 0.100]TT
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Pumping and Compression

Heuristic 43: To increase the 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:
 = P2VdP
W ∫P 1

It follows that it is more

efficient to pump a liquid than
to compress a gas. Thus, it is
almost always preferable to
condense a vapor, pump it, and
vaporize it, rather than
compress it.
Exception: if condensation
requires refrigeration.
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Pumping and Compression

Example : Feed Preparation of Ethylbenzene

Ethylbenzene is to be taken from storage at
25 °C and 1 atm and fed to a styrene
reactor at 400°C and 5 atm at 100,000 lb/h.

Show two alternatives for positioning the

temperature and pressure-increase
operations.

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Process Design Heuristics - Summary

We have focused on 16 design heuristics (out of 53 in the
book), enabling you to:
Understand the importance of selecting reaction paths that do
not involve toxic or hazardous chemicals, or to reduce their
presence by shortening residence times in the process units and
avoiding their storage in large quantities.
Be able to distribute the chemicals in a process flowsheet, to
account for the presence of inert species, to purge species that
would otherwise build up to unacceptable concentrations, to
achieve a high selectivity to the desired products.
Be able to apply heuristics in selecting separation processes to
separate liquids, vapors, and vapor-liquid mixtures.
Be able to distribute the chemicals to remove exothermic heats
of reaction.
Understand the advantages of pumping a liquid rather than
compressing a vapor.

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Process Design Heuristics - Sources

Parting Thought – When working on design projects,
students need to be made aware of important sources of
heuristics;e.g.,
Walas, S. M., Chemical Process Equipment – Selection and 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.

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