CHEMICAL PROCESS DESIGN

Supplemental Chapter: Process Design

Guidelines
 Materials of this chapter are based on the following two textbooks:

1. Turton, Bailie, Whiting, and Shaeiwitz. (2012). Analysis, Synthesis

and Design of Chemical Processes, Fourth Edition; Chapter 6 –
Understanding Process Conditions
2. Seider, W. D., Seader, J. D., Lewin, D. R., & Seider, W. D. (2016).
Product and Process Design Principles: Synthesis, Analysis, and
Evaluation, Fourth Edition; Chapter 6 - Heuristics for Process
Synthesis
 Part 1: Understanding Process
Conditions
Reference for this part: Turton, Bailie, Whiting, and Shaeiwitz. (2012).
Analysis, Synthesis and Design of Chemical Processes, Fourth Edition.
Chapter 6 – Understanding Process Conditions
 Outline
• Heuristics for Process Conditions
– Temperature
– Pressure
– Materials of construction (M.O.C)
• Examples of operation outside of heuristics
 Heuristics
• Temperature
< 40ºC > 250ºC > 400ºC
Require Require Require
refrigeration fired heater special M.O.C
• Pressure
< 1 atm > 10 atm
need vacuum Thick Walls - $
 Temperature
• T < 40º C – Refrigeration
– Use as much cooling water (cw) as possible,
minimize the use of refrigerated water (rw)

cw rw

– Operating Costs
• Cooling Water (30 – 40°C) $0.354/ GJ
• Refrigerated Water (5 – 15°C) $4.43/ GJ
 Temperature
40
35
Refrigeration (cw = 1)
Relative Cost of

30
25
20
15
10
5
0
-50 -30 -10 10 30 50
Temperature of Refrigerant
 Temperature
• T > 250ºC: use of high pressure (HP) Steam @ 260ºC (600
psig) as the hot stream to supply heat for a cold stream
(with required outlet temperature T > 250ºC) in a heat
exchanger (e.g. a shell and tube heat exchanger) is
impossible
– Use hot oil instead (hot oil as the hot stream in an
exchanger) or use a furnace. In both cases, use of
furnace is obligatory
• Fired Heaters are very expensive
 Temperature
Use a furnace to heat-up
Hot Oil Return
the hot oil in the circulation
loop of hot oil
Fuel Process
FURNACE
Hot Oil Flow

– CBM (bare module cost)

• Heat Exchanger = $ 1.70x105
• Fired Heater = $ 1.81x106
 T > 400º C
– M.O.C. is very important (use expensive
special alloy for high temperature condition)
 Pressure
• Vacuum
– Slightly Higher Cost due to Stiffening Rings
– Large Equipment
– Air Leaks

• High Pressure
– Thick Walls - $

– H2 Embrittlement

– Safety
 Material of Construction

• Carbon Steel
– Cheap
• Stainless Steel
– Expensive
– Better Chemical/Thermal Resistance
• What About T = 700 – 900ºC?
– Insulate inside of Pipe
– Metal – Refraction Lining
 Conclusions

• T < 40ºC – Refrigeration

• T > 250ºC – Fired Heater or Furnace
• T > 400ºC – M.O.C. Issues
• P < 1 atm – Vacuum and Large Equipment
• P > 10 atm – Thick wall, high cost
 Operating Conditions
Wall Thickness Increases

10 atm
Requires Requires Requires
Refriger- Fired Special
ation Heater M.O.C.

1 atm

40º C 250º C 400º C

Vacuum – Large Equipment
Do we ever operate outside these
limits?
• Tables 6.1 – 6.3
– Reactors and Separators
• Table 6.4
– Other Equipment
 Examples
• Example 1 – Acrylic Acid
– Fig B.10.1
– Why does T–305 Operate with the top pressure at 0.07 bar?
– Feed – 86.6 kmol/h Acrylic Acid – nbp =140°C
6.1 kmol/h Acetic Acid – nbp = 118°C
Table 6.2 – Reasons for using P<1 atm
1. Obtain a gas phase for VLE
2. Temperature sensitive materials
 Examples
• Example 2 – Separation of Propane
– Typical depropanizer operates at 220 psig (16
bar) – why?
Table 6.2 – reasons for using P>10 bar
1. Obtain a liquid phase for VLE
 Summary
• In general, using conditions close to
ambient temperature and pressure are
desirable from an economic and often
safety point of view.
• Operation outside of these “ideal”
conditions is acceptable but must be
justified from a process perspective.
 Part 2: Heuristics for Process
Synthesis
Sources of information for this part:

1. Seider, W. D., Seader, J. D., Lewin, D. R., & Seider, W. D. (2016).

Product and Process Design Principles: Synthesis, Analysis, and
Evaluation, Fourth Edition; Chapter 6 - Heuristics for Process
Synthesis

2. Couse materials from course CHEN 4470 – Process Design Practice, by

Dr. Mario Richard Eden, Department of Chemical Engineering, Auburn
University
 Heuristics for Process Synthesis - Objectives

 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.
 Raw Materials & Reactions
Heuristic 1: Select raw materials and chemical
reactions to avoid, or reduce, the
handling and storage of hazardous and
Example: toxic chemicals.
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
 Alternative EG Processes

 Use chlorine and caustic in a single reaction step,

to avoid the intermediate:
O
H
OH
C
H
2=
C
H+
2Cl
2+2
N
aO
H(
a
q)C
H
2C
H+
22N
a
C
l (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
 Distribution of Chemicals
1:8
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 excess ethylene in DCE
production
 Distribution of Chemicals
2:8
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
Example: removed.
 Distribution of Chemicals
3:8
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
 Distribution of Chemicals
4:8
Heuristic 4: Introduce liquid/vapor purge streams to
provide exits for species that
 enter process as impurities in the
feed
 produced by irreversible side-
reactions
when these species are in trace
Example: quantities and/or difficult
Ammonia synthesis loop to separate
from other species.

Note: Purge flow rate selection depends on economics!

 Distribution of Chemicals
5:8
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/hazardous
species.
Example: Catalytic converter in car exhaust
system.
 Distribution of Chemicals
6:8
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.
Often small quantities of chemicals are produced
in side-reactions.
• 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. In
so doing, it is often said that undesired byproducts are
 Distribution of Chemicals
7:8
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-
Example: Manufacture
case design. of allyl-chloride.
Example: Allyl Chloride 1:2

Kinetic data
HR ko
Reaction 3 2
E/ R (oR)
Btu/ lbmole lbmole/ (hr ft atm )
1 -4,800 206,000 13,600
2 -79,200 11.7 3,430
3 -91,800 4.6 x 108 21,300
Example: Allyl Chloride 2:2

9.60E-04

9.70E-04

9.80E-04

9.90E-04

1.00E-03

1.02E-03
1.01E-03
9.70E-4 < 1/T < 9.85E-4

-0.4 1015 < T < 1030

-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 ?
 Distribution of Chemicals
8:8
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 EtOAc with reactive

distillation
EtOH + HOAc 
 EtOAc + H2O

Conventionally, this would call for

reaction, followed by separation of
products using a sequence of separation
towers.
Reactive Distillation

EtOAc

HOAc
Reaction
zone
EtOH

H 2O


EtOH + HOAc  EtOAc + H2O
 Separations 1:3
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.
 Separations 2:3
Heuristic 10: Attempt to condense vapor mixtures
with cooling water. Then, use Heuristic
9.
Select from partial
Ref: Douglas (1988) condensation,
cryogenic
distillation,
absorption,
adsorption,
membrane
separation, etc.
Select from
distillation,
enhanced
distillation,
stripping towers,
Attempt to cool liquid-liquid
reactor extraction, etc.
products using
cooling water
 Separations 3:3
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
 Heat Transfer in Reactors
1:5
Although heat transfer in reactors is better discussed in
the context of heat and power integration, it is treated
here because many methods dealing with heat transfer
in reactors also affect the distribution of chemicals. First,
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
 Heat Transfer in Reactors
2:5
Heuristic 21: To remove a highly-exothermic heat of
reaction, consider the use of….

excess reactant

an inert diluent

cold shots
 Heat Transfer in Reactors
3:5
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.
 Heat Transfer in Reactors
4:5
Example: TVA design for NH3 synthesis converters
 Heat Transfer in Reactors
5:5
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.
 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.
Pumping or compression work is W 
P
P2 
VdP
1
given by:
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.
 New Heuristics in 4th Edition
Heuristic 12-20: Separations involving solid particles,
e.g. crystallization, multiple effect
evaporators, centrifugation and
others.
Heuristic 25-33:
Heat exchangers, furnaces, fired
Heuristic 34-42: heaters.

Heuristic 43-47: Pumping, compression, pressure

reduction.
Heuristic 48:
Vacuum.
Heuristic 49-53:
Conveying granular solids
 Summary – Design
Heuristics
Covered in detail 16 design heuristics, 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.
 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.
 Apply heuristics in selecting separation processes to separate
liquids, vapors, and vapor-liquid mixtures.
 Distribute chemicals to remove exothermic heats of reaction.
 Understand the advantages of pumping a liquid rather than
compressing a vapor.