CCB 3024

PROCESS PLANT DESIGN

Conceptual Process Design

Synthesis of Reaction System (2)

Lecturer : Dr Abrar Inayat

At the end of this lecture, student should be able to ;

1. Select appropriate reactor system according to the reaction system

2. Specify suitable range for the design/operating parameter of reactors
3. To know about the mathematical approaches for reactor network

HEURISTIC

Polymerisation reaction ......

Polymers are characterised by the distribution of molecular weight.

2 broad types of reaction
1. Reactions with Termination steps
eg.polymerisation of Vinyl Chloride
R + CH2 = CHCl ------> RCH2 - CHCl
initiator

vinyl chloride

CH3 or
OH

vinyl chloride free radical

propagates

RCH2 - CHCl + CH2 = CHCl ------> RCH2 - CHCl - CH2 - CHCl

leading to

R - (CH2 - CHCl)n - CH2 - CHCl

Polymers
Reaction terminated by
the joining of these molecules

Question ?
How do we
select suitable
type of reactor
for such
reaction ?

HEURISTIC

Important note for the reaction :

The active polymer life is short as compared to

the average residence time in reactor.
RCH2 - CHCl + CH2 = CHCl ------> RCH2 - CHCl - CH2 - CHCl

leading to

R - (CH2 - CHCl)n - CH2 - CHCl

Polymers

Reaction terminated by
the joining of these molecules

The length of the chain depends on

concentration of free radical available
in the reactor. The concentration of the
free radical decreases as reaction proceed
with time. Therefore, at beginning due to
presence of high concentration of free radical,
polymer chain tend to be shorter. As reaction time
proceeds, lesser free radical concentration thus
harder for termination steps to take place resulting
in longer chain molecule.

Best to choose CSTR.

CSTR

HEURISTIC

2. Reactions without Termination Step.

eg.polycondensation
HO - (CH2)n - COOH + HO - (CH2)n - COOH
--------> HO - (CH2)n - COO - (CH2)n - COOH + H2O

In this reaction, the polymer grows by successive esterification with

elimination of water and no termination step.
Question ?
How do we select suitable type of reactor for such reaction
The active polymer life is long compared to the average residence
time in reactor. It is highly desirable for all the molecules to have
almost similar residence time to produce polymer of similar chain
length. Therefore, control of residence time is important.
Best to choose PLUG FLOW

PLUG FLOW

Example on Reactor Selection

Given the following reaction systems to produce product C, select a suitable reactor for the system.

A+BC

rC = k1 CA0.5 CB2

CD

rD = k2 CC2

A+BD

r D = k 3 CA CB

Mixture of series parallel reactions

Analysing the parallel reaction

A+BC

rC = k1 CA0.5 CB2

A+BD

r D = k 3 CA CB

r3
=
r1
r3
=
r1

1-0.5
1-2
k3
CA
CB
k1
0.5
-1
k3
CA
CB
k1

What reactor configuration should be selected?

r3
=
r1
r3
=
r1

1-0.5
1-2
k3
CA
CB
k1
0.5
-1
k3
CA
CB
k1

B
Semi CSTR

OR
Analysing the series reaction

A+BC

rC = k1 CA0.5 CB2

CD

rD = k2 CC2

REACTANT A

REACTANT B

Control of residence time is important.

Therefore choose plug flow.

SEMI PLUG FLOW

Reactor Operating Parameter

In the preceding lecture, the choice of the reactor is made based on the most appropriate
concentration profile as the reaction progressed. However, there are still important effects that need
to be considered i.e., the reactor operating parameter.
Besides looking at the reaction system, the other aspects governing chemical reaction which have
to be considered are;
1. Reaction Equilibrium for reversible reaction.
Pressure Effect

aA + bB cC + dD

The extent of reaction which can be calculated using Gibbs Free Energy

0 = ln
=
=

where

For gaseous reaction

For liquid reaction

Eg : Given reaction below at 1 bar, 300 K to produce Ammonia NH3. Feed is according to the stoichiometric ratio.

3 H2 + N2 2 NH3
Given the data for Std. Free Energy of Formation
Assume ideal gas law

H2
N2
NH3

a. Determine Ka equilibrium constant

ln =

(2 16,223 0 0 )
ln =
= 13.008
8.314 300
= 4.4597
=

105

2 3 .2

Initial moles
Equilibrium moles

2 3 .2

0
300 (
)

0
0
-16.223

H2

N2

1-X

2X

3-3X

NH3

Total moles at equillibrium = 4 2X

Mole Fraction

3-3X

1-X

2X

4-2X

4-2X

4-2X

Eg : Given reaction below at 1 bar, 300 K to produce Ammonia NH3. Feed is according to the stoichiometric ratio.

3 H2 + N2 2 NH3

H2

N2

NH3

3-3X

1-X

2X

4-2X

4-2X

4-2X

b. Composition of the reaction products at equilibrium

3 2
2 3 .2

3 2
2 3 .2

3 2
2 3 . 2

Mole Fraction

16 2 2 2
=
27 1 4

for P = 1 bar

X = 0.97 bar
Therefore the composition at equilibrium is ;
H2
N2
NH3

[3 3 (0.97)] / [4 2 (0.97)] = 0.0437

[1 (0.97)] / [4 2 (0.97)] = 0.0146
[2 (0.97) / [4 2 (0.97)] = 0.9418

Besides looking at the reaction system, the other aspects governing chemical reaction which have
to be considered are;
aA + bB cC + dD
2. Reaction Equilibrium for reversible reaction.
Temperature Effect (Endothermic & Exothermic Reaction)
The extent of a reaction is influenced by temperature can be calculated using enthalpy of formation through the
relation developed from Gibbs Free Energy

Integrate the above relation ;

0
ln
= 2 =

from

0 = ln

2
0 1
1
=

1
2
1

The effect of temperature on reaction equilibrium could be determined since the std. heat of reaction is available
in thermodynamics data.

0 = 0 + 0 0 0
For exothermic reaction the DH0 is < 0 while for endothermic reaction the DH0 is > 0
For exothermic reaction, higher temperature will shift the equilibrium to reactant side while
For endothermic reaction, higher temperature will shift equilibrium to product side.

Besides looking at the reaction system, the other aspects governing chemical reaction which
have to be considered are;
3.

Rate of Reaction - Temperature Effect.

aA + bB cC + dD

The effect of temperature on rate of reaction can be computed from the Arhennius equation.

= 0
Expanding the equation

2 1
1
=

1 1
2

E is the activation energy

Generally, the higher the temperature, the higher is the reaction rate.

DESIGN PROCEDURE FOR REACTOR OPERATING PARAMETER.

HEURISTIC

3. Decide on the Reaction Condition - operational parameter.

Let's consider concentration of reactants in the reactor
Some possibilities to consider

EXCESS OF ONE REACTANTS

ADDITION OF INERTS

This can force the reaction of a selected

component to completion due to certain
reason.

This can favour reaction to proceed

towards favorable direction.

eg. C2H4 + Cl2 ---> C2H4Cl2

Cl2 is difficult to separate. Add excess of C2H4 to
force complete reaction of Cl2

eg. Feed <==> Prod1 + Prod2

Rxn. cause an increase in no. of moles. Adding
inert cause reduction in no. of moles/vol.
Therefore rxn. proceed to produce more products.

HEURISTIC

Let's consider concentration of reactants in the reactor (cont...)

Some possibilities to consider

REMOVAL OF PRODUCT

RECYCLE UNWANTED BYPRODUCTS

This can get the reaction to proceed to

the favorable direction.
eg. 2SO2 + O2 2SO3

eg. Feed1 + Feed2 Product

Feed1 + Feed2 Byproduct

Intermediate removal of Sulfur trioxide will

make the reaction towards producing more
products. But how?

absorption

Rxn 2

H2O

H2O

This can surpress the formation

of more unwanted by-products.

Recycling byproduct will suppress

reaction 2 thus avoiding waste of feed material

absorption

HEURISTIC

Let's consider concentration of reactants in the reactor (cont...)

Consider more complex reaction !

Multiple reactions in parallel producing byproducts

a1

b1

a2

b2

Feed1 + Feed2 ------> Product (s)

Rxn 1 : r1 = k1 Cfeed1 Cfeed2

Feed1 + Feed2 ------> Byproduct (s)

Rxn 2 : r2 = k2 Cfeed1 Cfeed2

ratio of secondary
to primary reaction

r2
=
r1

a2 -a1
b2 -b1
k2
Cfeed1
Cfeed2
k1

Even after reactor selection was made, there are still opportunities for maximising selectivity !
1. If (a2-a1) > (b2-b1), use excess Feed2 and if (a2-a1) < (b2-b1), use excess Feed1
2. If reaction 2 is reversible, increasing inerts concentration will decrease byproduct formation.
3. Recycling the byproducts to the reactor will suppress the formation of more byproducts
if the reaction is reversible.

HEURISTIC

Multiple reaction in series producing byproducts.

a1

Feed(s) -------> Product

Rxn 1 : r1 = k1 Cfeed

Product -------> Byproduct(s)

Rxn 2 : r2 = k2 Cproduct

a2

Formation of byproducts is minimise by keeping the product composition low in the reactor.
Option that can be considered :
Use of 3rd component which does not participate in the reaction to produce byproducts
Intermittent/intermediate removal of products as reaction takes place.
eg.
C6H5CH3 + H2 -------> C6H6 + CH4
2C6H6 <====> C12H10 + H2

The use of excess Hydrogen

helps to minimise formation
of diphenyl.

HEURISTIC

Mixed parallel and series reactions producing byproducts

Feed(s) -------> Product
Feed(s) -------> Byproduct(s)
Product -------> Byproduct(s)
a1

Feed(s) ------> Product(s)

Rxn 1 : r1 = k1 Cfeed

Feed(s) ------> Byproduct(s)

Rxn 2 : r2 = k2 Cfeed

Product ------> Byproduct(s)

Rxn 3 : r3 = k3 Cproduct

a2

a3

Options that can be considered ;

The use of excess 3rd component which does not involve in reaction to produce byproduct
can suppress the byproduct formation by keeping product composition low.
Recycling of byproducts if the reaction is reversible can assist in minimising byproduct
formation.

SUGGESTED PROCEDURE (cont...)

HEURISTIC

3. Decide on the Reaction Condition - operational parameter.

Let's now consider temperature for the operation of the reactor.
Generally, there are several critical temperature limits that apply to chemical processes. At elevated
temperatures, common construction materials (primarily carbon steel), suffer a significant drop in
physical strength and must be replaced by a more costly material.
Turton et al., Analysis, Synthesis and Design of Chemical Processes 1998
Tensile Strength of Material (bar)
Temperature

Ambient

400 C

550 C

1190
1290

970
1290

170
430

Carbon Steel (grade 70)

Stainless Steel (Type 302)

A decision to operate above 400 C must be justified in view of the material limitation.
Turton et al., Analysis, Synthesis and Design of Chemical Processes 1998

From utility perspective, a decision to operate outside the range of 40 C to 260 C requiring
special heating/cooling media, has to be justified. Within this range, normal steam and cooling
water could be utilised easily.

SUGGESTED PROCEDURE (cont...)

HEURISTIC

3. Decide on the Reaction Condition - operational parameter.

Let's now consider temperature for the operation of the reactor.
How do we decide ?
SINGLE REACTION
Endothermic Rxn

MULTIPLE REACTIONS
For Parallel/Series Reaction

Set T as high as possible

Good for rate of reaction
So what is the limit ?
Exothermic Rxn
Set T low to take advantage on
conversion in a reversible reaction.
Not good for rate of reaction
Need to compromise !

A ---> B ---> C
k1

B product

k2

if k1 increase more than k2 w.r.t. T, then go for as

highest T as possible.
if k2 increase more than k1 w.r.t. T, then go for as
lowest T as possible. Careful, as need to compromise.
The main issue is how to control T effectively.
Can you suggest a number of ways to do that.

So what is the compromise ?

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SUGGESTED PROCEDURE (cont...)

3. Decide on the Reaction Condition - operational parameter.

HEURISTIC

Let's now consider pressure for the operation of the reactor.

There are economic advantages associated with operating equipment at higher pressure when
gases are present i.e., decrease in gas volume. This tend to reduce the size of equipment to give
the required residence time. Most chemical processing equipment can withstand pressures up to
10 bar without additional capital investment. Beyond 10 bar, thicker walls for the equipment
vessel is required thus contributing to higher cost.
Likewise operating below ambient pressure causes equipment size to be larger and thus
increased in capital cost.

A decision to operate outside the pressure range of 1 to 10 bar must be justified.

Turton et al., Analysis, Synthesis and Design of Chemical Processes 1998

HEURISTIC

SUGGESTED PROCEDURE (cont...)

3. Decide on the Reaction Condition - operational parameter.

Let's now consider pressure for the operation of the reactor.
For vapour phase reaction....
SINGLE REACTION
Decrease in number of moles
Pressure decreases as reactant/s
were converted to products
Increase pressure to take advantage.

For liquid phase reaction,

pressure is known to have
little effect. Why?

MULTIPLE REACTIONS
The same general guideline can be used but
consideration has to be given when having
competing reaction producing byproducts.
Selectivity has to be taken into account !

Increase in number of moles

Pressure increases as reactant/s
were converted to products
Decrease pressure to take advantage

11

HEURISTIC

SUGGESTED PROCEDURE (cont...)

4. What about reactor phase?

Given the fact that the temperature and pressure
has been decided normaly, the phase can be
determined directly !

The preferences if possible ---> liquid phase reactor !

Higher density thus higher concentration

per volume size
Smaller Reactor Volume

However, depends on other matters

- Rate of mass/Heat transfer
Gas phase might have
better transfer of heat & mass

- Safety consideration

Not so much of an important criteria !

SUGGESTED PROCEDURE (cont...)

HEURISTIC

5. Catalyst Selection.
Function of Catalyst :
increase rate of reaction without changes in quantity and composition
at the end of reaction.
Homogenous Catalyst
may modify reaction mechanism by
participating in the reaction but regenerated
back in the subsequent step.
eg. production of ketene from acetic acid.
CH3COOH ----> CH2=C=O + H2O

Heterogenous Catalyst
- Catalyst differ in phase from reacting species
- Most oftenly solid
- Reacting species diffuse to surface of catalyst and
are adsorped. Reaction takes place and products
then desorb and diffuse back to bulk gas/liquid.
- Effective surface area on catalyst which depends
on catalyst porosity is an important consideration.

use triethyl phospate as a

catalyst.
problem : possible loss of catalyst due
to imperfect separation to recover
catalyst.

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Example (Text by Smith R. pg. 80)

Given the reaction below for the production of monoethanolamine;

Ethylene oxide + ammonia monoethanolamine
Monoethanolamine + ethylene oxide diethanolamine
Diethanolamine + ethylene oxide triethanolamine

Side reaction
Side reaction

Select a reactor that will maximise the production of monoethanolamine.

Plug Flow to control residence time.

Suggest option for the operational condition which could further maximise the production.

Excess Ammonia
Intermediate removal of Monoethanolamine.

Example.

tert-Butyl hydrogen sulfate is produced from the reaction below;

Iso-butylene + sulfuric acid tert-butyl hydrogen sulfate
tert-butyl hydrogen sulfate + water tert-butyl alcohol + sulfuric acid
The primary reaction is rapid and exothermic. Laboratory studies indicate that the reactor
yield is a maximum when the concentration of sulfuric acid is maintained at 63 percent.
The temperature should be maintained around 0 oC to avoid excessive formation of
byproducts.
Make the choice of the reactor.
Sulfuric acid

13

Recall the following slide again.....

SELECTION OF REACTOR

During the conceptual design of a chemical process, among the related decisions that
have to be made concerning reactor ;

Reactor Type and/or Network

CSTR OR BATCH

Operating Conditions

TEMPERATURE
PRESSURE
CONCENTRATION
INERT
CATALYST

CSTR

PLUG FLOW

RECYCLE REACTOR

PLUG FLOW

?
RECYCLE REACTOR

PLUG FLOW

REACTOR VOLUME
AND ORIENTATION

RECYCLE REACTOR

CSTR

HOW DO WE
DECIDE ?

we have look at tackling this using heuristic approach !

Synthesis of Reactor Network Mathematical Programming Approach

We have seen a number of guidelines developed to conceptually design reactor.
Limitations will appear when having to deal with complex reactor configuration/network.
Simple reaction

Highly Complex reaction

straight forward thus

simple guideline will do.

complicated with conflicting in guideline.

require complex reactor - network of reactor !

A B
B C
simple plug flow reactor

A + B C D
A + C E
B + D F

exotherm. rxn
endotherm. rxn
endotherm. rxn

D is the product !
Could be ;

Flow Pattern
Mixing Location
Heating & Cooling

How can we derive such configuration

or network just from the heuristic guideline ?
The method that can deliver this will need extensive mathematics and programming
- Mathematical Programming Approach.

14

MATHEMATICAL

But how do we go about doing this ?

Recall the key info. required when designing reactor
Reaction Chemistry

Reaction Kinetics

For simple reaction chemistry, selection of

reactor can be done using the heuristic guideline
even without the reaction kinetics.

But for complex reaction chemistry, since

mathematical programming approach is
to be adopted, detailed reaction kinetics now
become important.

Still the important parameters that decide the reactor network are ;

Conversion
Selectivity

Selectivity normally becomes the more dominant one.

Recall the mathematical programming approach that was introduced earlier.

Generate a super structure containing all alternatives and optimised it

in order to produce the optimal solution.

SUGGESTED PROCEDURE

MATHEMATICAL

Formulate/Generate a super structure which contains all possible candidates for the
solution of the optimal reactor. Then solved it mathematically.
The superstructure is created mathematically.
How do we identify all the possible candidates for the solution ?
One Option : Use the method of Geometric Concepts for Attainable Region
Biegler, Grossman & Westerberg,
Synthesis Methods of Chemical Process Design pp 438 - 447
For chemical reactor networks, the attainable region concept was first presented
by Horn (1964) who noted that ;
...variable such as recycle flowrate and composition of the product form a space which in
general can be divided into an attainable region and a non-attainable region. The attainable
region corresponds to the totality of physically possible reactors ... Once the border is known
the optimum reactor corresponding to a certain environment can be found by simple geometric
considerations.
Horn F., (1964). Attainable Regions in Chemical Reaction Technique. In the
3 rd European Symposium on Chemical Reaction Engg. London: Pergamon.

15

To briefly understand how it works,

MATHEMATICAL

Consider a reaction A B C

B
C

Time

MATHEMATICAL

A BC
CB
F

CSTR
PLUG FLOW
E
H

CA
For a PFR with variable residence time and fixed feed C A0 and CB0, one can solve
the ordinary differential equations from the feed point :

dCA / dt = rA
dCB / dt = rB

dCB / dCA = rB / rA

From this differential eqn.,

we can plot the trajectory for
HEGF

16

MATHEMATICAL

Consider a reaction A --> B ---> C

CB
F

CSTR
PLUG FLOW
E
H

CA

For a CSTR, the path from the feed can be generated using the equations:
CA - CA 0 = t r A

CA - CA 0

CB - CB 0 = t r B

CB - CB 0

= rA / rB

From this eqn., we can plot the

trajectory for GH

Note that in the two cases above, we assume a fixed feed, an initial temperature and trajectories
that are determined entirely by the state eqns. derived for concentration as shown above. This is
true unsteady state for isothermal or adiabatic systems.

MATHEMATICAL

How do we plot the attainable region ?

CB

Plot the attainable region using reaction/rate

vectors. The eqn. for the vectors are obtained
from the plug flow and/or CSTR trajectory
as shown earlier.

F
G

CSTR
PLUG
FLOW
E

dCB / dCA = rB / rA

plug flow

CA

CA - CA 0
CB - CB 0

= rA / rB

CSTR

Example 13.3 page 443 : Systematic Methods of Chemical Process Design

Biegler, Grossman & Westerberg.

illustrates the application of the method !

17

MATHEMATICAL

The attainable region will assist in setting the super structure for the mathematical
programming approach in the sense that it can provide engineer with the family of solutions for
the problem related to reactor network. This will significantly reduces the number of options
that have to be dealt by the mathematical programming during optimisation.

Hence the task of determining this,

SELECTION OF REACTOR

During the conceptual design of a chemical process, among the related decisions that
have to be made concerning reactor ;

Reactor Type and/or Network

CSTR OR BATCH

PLUG FLOW

RECYCLE REACTOR

REACTOR VOLUME
AND ORIENTATION

Operating Conditions
TEMPERATURE
PRESSURE
CONCENTRATION
INERT
CATALYST

CSTR

RECYCLE REACTOR

PLUG FLOW

PLUG FLOW

RECYCLE REACTOR

CSTR

HOW DO WE
DECIDE ?

is made simpler !

Conclusions
We have looked at the followings;

Selection of Suitable Reactor for a Specified Reaction System : Plug flow, CSTR,
Hybrid of Plug Flow and CSTR.
Determination of Suitable Reactor Operating Parameter : Temperature, Pressure,
Reactant Concentration etc.
Mathematical approach for reactor synthesis

18

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