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LECTURE 3
HEURISTICS FOR PROCESS SYNTHESIS

Introduction

 We have applied heuristics in the synthesis of vinyl chloride


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

 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.,
g by y simulation)) to ensure that they
y
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.
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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.
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

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).

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Alternatives

n 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)

o Or as ethylene-oxide is formed in R.1, react it with carbon


dioxide to form ethylene-carbonate,
y , 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)
5 CH2 CH2

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

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To completely consume the hazardous and toxic reactant (chlorine)

To absorb excess heat of reaction hence maintaining moderate


temperature

Minimize side reactions.

Chemical Cost (cents/lb)


Ethylene 18
Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0
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Heuristic 3:  When nearly pure products are required,


eliminate inert species before the reaction,
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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Need to decide whether to


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

or after reaction...

Clearly, the ease and cost of the separations


must be assessed.
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
t lli ti
Permeability and selectivity for
membrane separation

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Heuristic 4: Introduce liquid or vapor purge streams to


provide exits for chemical 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


off Ar
A and
d CH4.
CH4

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

Alternatives for separating traces species cannot


be totally rule out

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
p to recover valuable species.
p
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
p or p
purged.
g Instead,, theyy
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
d i d products.
desired d t IIn ththe initial
i iti l distribution
di t ib ti off
chemicals, assume that these conditions can be
satisfied - obtain kinetics data and check this
assumption before developing a base-case
design.

Example:
p Manufacture of allyl-chloride
y
-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

ln(k) -0.8

-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
removingg the pproducts,, and hence,, driving
g the
reactions to the right.

Example: Manufacture of Methyl-acetate using reactive


distillation.
Conventionally, this would call for reaction:
M OH + HOAc
MeOH HOA M
MeOAc
OA + H2O,
O

followed by separation of products using a


sequence of separation towers.

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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, liquid-liquid extractors,
crystallization
y and adsorption.
p

Select from
distillation,
Example: enhanced
distillation, stripping
Product from reactor is liquid towers, liquid-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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Example: Product from reactor is vapor Select from partial


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

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

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Example: Products from reactor are in liquid and vapor phases

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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.
intercoolers

Endothermic reactors are treated similarly

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Endothermic reactors are treated similarly:

Heuristic 23: To control temperature for a highly-endothermic


heat of reaction,
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
j k t d vessell or heating
jacketed h ti coils.
il Also,
Al consider
id
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 gasgas.

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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