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PSE

HEURISTICS FOR PROCESS

SYNTHESIS

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

INTRODUCTION

Recalling the process operations in process synthesis:

Chemical reaction
Mixing and recycle
Separation
Temperature, pressure and phase change
Task integration

We have applied heuristics in the synthesis of vinyl chloride

PFD such as using pump instead of compressor in order to
increase stream pressure.

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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.

Heuristics usually lead to profitable design, but we need to

be watchful for situation in which they might lead to
suboptimal design.

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: Two-step Manufacture of Ethylene Glycol (EG).

O
1 (R.1)
C2H4 + -2 O2 → CH2 - CH2

O OH OH
CH2 - CH2 + H2O → CH2 - CH2 (R.2)

Remember: Inherent safety

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 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.

 Since both reactions are highly exothermic, they need to be

controlled carefully.

 A water spill into an ethylene-oxide storage tank could lead to an

accident similar to the Bhopal incident.

 So the main issue here is the risk associated with the storage of
hazardous intermediate (ethylene-oxide).

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

avoid the storage for intermediate but higher raw material cost:

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

 Or as ethylene-oxide is formed in R.1, 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 dichloroethane
production

 To completely consume the hazardous and toxic reactant (chlorine)

 To absorb excess heat of reaction hence maintaining moderate

temperature

 Minimize side reactions.

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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:

Need to decide whether to

remove inerts (i.e. D) before
reaction...

… or after reaction...

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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

Volatility difference for distillation

Difference in freezing point for
crystallization
Permeability and selectivity for
membrane separation

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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.

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Recirculation without purging will lead to build-up

of Ar and CH4.

Here the purge stream contains Ar, CH4, N2, H2

Note: Purge flow rate selection depends on

economics!

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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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Heuristic 6: By-products that are produced in reversible

reactions, in small quantities, are usually not
recovered in separators or purged. Instead, they
are usually recycled to extinction.

When the reaction proceeds irreversibly, small quantities of by-

products must be purged, otherwise they will buildup in the
process continuously until the process must be shut down.

When, however, the reaction proceeds reversibly, it becomes

possible to achieve an equilibrium conversion at steady state by
recycling product species without removing them from the
process. It is often said that undesired byproducts are recycled
to extinction.

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Heuristic 7: For competing series or parallel reactions, adjust

the T, P, 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

-An example of series-parallel reaction
-The desired product is allyl-chloride.

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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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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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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.

Example: Manufacture of Methyl-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

HOAc
Reaction
zone
MeOH

H2O

MeOH + HOAc ↔ MeOAc + H2O

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Separations

Heuristic 9: Separate liquid mixtures using distillation and

stripping towers, liquid-liquid extractors,
crystallization and adsorption.

Select from
distillation,
enhanced
distillation, stripping
Example: towers, liquid-liquid
Product from reactor is liquid extraction, etc.

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Heuristic 10: Attempt to condense vapor mixtures with cooling

water. Then, use Heuristic 9.

Heuristic 11: Separate vapor mixtures using partial condensers,

cryogenic distillation, absorption towers,
adsorbers, and/or membrane devices.

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Select from
Example: Product from reactor is vapor partial
condensation,
cryogenic
distillation,
absorption,
adsorption,
membrane
separation, etc.

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

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Heat Transfer in 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.

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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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Endothermic reactors are treated similarly:

Heuristic 23: To control temperature for a highly-endothermic

heat of reaction, consider the use of excess
reactant, an inert diluent, and hot shots. These
affect the distribution of chemicals and should be
inserted early in process synthesis.

Heuristic 24: For less endothermic heats of reaction, circulate

reactor fluid to an external heater, or use a
jacketed vessel or heating coils. Also, consider
the use of interheaters.

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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:

P2
W& = ∫ V&dP
P1

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 It follows that it is more efficient (cheaper) 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.

 Example: If we want to turn low pressure liquid stream to a high

pressure vapor stream, we should increase the pressure first with
a pump and then vaporize the high pressure liquid.

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SUMMARY

 Select reaction paths that do not involve toxic or hazardous

chemicals, and avoiding their storage in large quantities.
 Purge species that would otherwise build up to unacceptable
concentrations, to achieve a high selectivity to the desired
products.
 Apply heuristics in selecting separation processes to separate
liquids, vapors, and vapor-liquid mixtures.
 Distribute the chemicals, by using excess reactants, inert
diluents, and cold shots, to remove the exothermic heats of
reaction.
 Advantages of pumping a liquid rather than compressing a
vapor.

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Make sure to review all 53 Heuristics

in Chapter 6

Thank you!

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