CDB 3044

PROCESS PLANT DESIGN

Conceptual Process Design - Synthesis of Reaction System (I)

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

1. Distinguish and differentiate the various reaction systems

2. Select appropriate reactor system according to the reaction system

3. Specify suitable range for the design/operating parameter of reactors

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 Fundamentals and Selection of Reaction System
What is chemical reactor ?
Chemical Reactors are used to produce high value chemicals from lower value chemicals.

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

Chemical Reactor is a device in which change in composition of matter occurs by chemical

reaction. The chemical reaction is normally the most important change, and the device is designed
to accomplish that change.
Missen et al., Chemical Reaction Eng. and Kinetics 1999

Why is chemical reactor such an important unit operation?

Good reactor performance is of paramount importance in determining the economic viability of the
overall design and fundamentally important to the environmental impact of the process.
Smith, Chemical Process Design 1995

The reactor network strongly influences the character of the entire flowsheet, and consideration on
the reactor network has a dominant effect on the improvement.
Biegler, Grossman & Westerberg, Systematic Method of Chemical Process Design 1997

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 Review on Chemical Reactions
Reaction System
Before we look at the reactor selection, we need to understand types of reaction system.
Single Reaction
Feed (s)  Product or
Feed (s)  Product + Byproduct (s)

Example i : Isomerization – without byproduct

Isomerisation is the process by which one molecule is transformed into another molecule which has
exactly the same atoms, but the atoms are rearranged e.g. A-B-C → B-A-C (these related molecules
are known as isomers).

Example ii : Production of Acetone from Isopropyl Alcohol – with byproduct

(CH3)2CHOH → CH3COCH3 + H2

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 Review on Chemical Reactions
Reaction System
Multiple Reaction in Parallel

Feed (s)  Product Feed (s)  Product + Byproduct 1

Feed (s)  Byproduct (s) Feed (s)  Byproduct 2 + Byproduct 3

Example : Production of ethylene oxide

Main reaction
CH2=CH2 + 3 O2 → 2 CO2 + 2 H2O Byproduct parallel reaction

2 (CH2CH2)O + 5 O2 → 4 CO2 + 4 H2O Byproduct parallel/series reaction

Multiple reaction will lead to lost of material, and in

some cases the byproduct could poison the catalyst.
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 Review on Chemical Reactions
Reaction System
Multiple Reaction in Series

Feed (s)  Product  Byproduct(s) Feed (s)  Product + Byproduct 1

Product  Byproduct 2

Example : Production of formaldehyde from methanol

2 CH3OH + O2 → 2 HCHO + 2 H2O Main reaction

A series reaction involving the formaldehyde

HCHO → CO2 + H2 Byproduct series reaction

The series reaction could also lead to the lost of material,

and at some cases the byproduct could poison the catalyst.

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 Review on Chemical Reactions
Reaction System
Mixed Parallel and Series Reactions.
Feed (s)  Product Feed (s)  Product
Feed (s)  Byproduct (s) Feed (s)  Byproduct 1
Product  Byproduct (s) Product  Byproduct 2
Example : Production of ethanolamines from ethylene oxide and ammonia
Monoethanolamine is produced by reacting ethylene oxide with aqueous ammonia; the reaction also produces diethanolamine
and triethanolamine. The ratio of the products can be controlled by changing the stoichiometry of the reactants.

monoethanolamine O
+
diethanolamine
O
+

triethanolamine

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 Review on Chemical Reactions
Reaction System
Polymerisation Reactions
Monomers are reacted together to produce a high molar mass polymer. There are 2 broad types of polymer reactions:

1. Reaction with Termination steps (Addition polymerisation or free radical polymerisation)

The polymerization process of Addition or Chain-Reaction Polymerization consists of three
steps: Initiation, Propagation and Termination; for example, manufacturing of polyethylene.

The monomer ethylene composed of two carbon atoms, each bonded to two hydrogen atoms and sharing a double
bond with one another.
Polyethylene consists of a chain of single-bonded carbon atoms, each still carrying its two hydrogen atoms.
The polymerisation to polyethylene involved "free radical polymerization”.
A catalyst (benzoyl peroxide )is used and when heated it is split into two fragments, each with one unpaired
electron, or free radical. These fragments are the initiator fragments. The unpaired electron seeks a convenient
target in the double bond between the carbon atoms from where it takes the electron and bonds itself to one of the
monomer's carbon atoms.
polyethylene

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 Review on Chemical Reactions
Reaction System
Polymerisation Reactions

The initiating reaction creates another free radical associated with the ethylene molecule's
of the other carbon atom. Ethylene monomers begin attaching themselves in a chain,
creating new radicals each time and lengthening the chain. This stage is called
propagation.

Growing chains may also attach themselves to one another. Eventually, free radical
polymerization stops due termination reactions.

Instead of stealing an electron from double-bonded carbons or a nearby propagating

chain, the carbon atom with the free radical sometimes steals an entire hydrogen atom
from another chain end. The polymer end, which is robbed of its hydrogen, easily forms a
double bond with its adjacent carbon atom, and polymerization stops.

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 Review on Chemical Reactions
Reaction System
Polymerisation Reactions

2. Reaction without Termination steps

The polymer grows by successive esterification with elimination of water (polycondensation) with no termination step.

Polycondensation takes place between two polyfunctional molecules to produce one larger polyfunctional molecule, with
the possible elimination of a small molecule such as water. The reaction continues until almost all of one of the reagents
is used up; an equilibrium is established which can be shifted at will at high temperatures by controlling the amounts of
the reactants and products.

The best known polyester being used as a film and as a fiber is called
poly(ethylene terephthalate) (PET).

HO-(CH2)n-COOH + HO-(CH2)n-COOH  HO-(CH2)n-COO- (CH2)n –COOH + H2O

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 Review on Chemical Reactors
Reactor Types There are several basic types of reactor:

REACTOR
RECYCLE REACTOR

CSTR
PLUG FLOW
PLUG FLOW
BATCH REACTOR
CSTR
Continuous CSTR
COMBINATION OF PLUG FLOW AND CSTR

CLASS DISCUSSION
And how do they differ ?

 Application type Consider simple reaction below,

 Operation wise A + B --------> C
 Conversion and
 Selectivity Performance

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 Review on Chemical Reactors
Consider a more complex reaction:

A + C  E + F E is the product
F + C  H

For such complex reaction case, Douglas (1998) noted that frequently the reaction kinetics cause the conversion
and selectivity to be in conflict with each other.

A low selectivity is achieved A high selectivity is achieved

with high reactor conversion with low reactor conversion
spectrum of operation

Concern is to get conversion and selectivity to be as high as possible.

Using single (simple) reactor will not allow high values on conversion and selectivity !

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 Review on Chemical Reactors
Looking back at the reaction:
A + C ====> E + F E is the product
F + C ====> H

Maintaining as high concentration of A & C will ensure high reaction kinetics.

What reactor would be suitable here….

PLUG FLOW

However, high concentration of C and F will lead to more production of H.

What reactor would be suitable here….

CSTR
So, what would be the suitable reactor here?

REACTOR NETWORK !

CSTR
PLUG FLOW
This is actually possible in a complex reactor unit - advanced design
CSTR
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 Review on Chemical Reactors
REACTOR FACTOR PERFORMANCE

REACTANT CONSUMED IN THE REACTOR

SINGLE PASS
REACTANT FED TO THE REACTOR
CONVERSION
REACTANT CONSUMED IN THE PROCESS
OVERALL
REACTANT FED TO THE PROCESS

DESIRED PRODUCT PRODUCED

SELECTIVITY
REACTANT CONSUMED IN THE REACTOR
× STOICHIOMETRIC
FACTOR

DESIRED PRODUCT PRODUCED

REACTOR YIELD
×
STOICHIOMETRIC
FACTOR
REACTANT FED TO THE REACTOR

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 Review on Chemical Reactors

CONVERSION
WHICH ONE DO YOU THINK IS MORE MEANINGFUL ?

SELECTIVITY REACTOR YIELD

CONSIDER : Unwanted formation of byproducts

Unreacted feed which are recyclable

High reactor conversions are neither necessary nor desirable for optimum reactor performance.
At low reactor conversions, high overall conversions can be achieved with increased recycle.

Competitions from undesired reactions limit conversion to the desired products.

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

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 Review on Chemical Reactors
Example – Calculation for reactor performance

Benzene is to be produced from Toluene based on the reaction;

C6H5CH3 + H2  C6H6 + CH4
But there is a side reaction to produce diphenyl;

2 C6H6  C12H10 + H2

Below is the composition of reactor feed and effluent;

Component Inlet Flowrate (kmol/hr) Outlet Flowrate (kmol/hr)

Hydrogen 1858 1583
Methane 804 1083
Benzene 13 282
Toluene 372 93
Diphenyl 0 4

Calculate conversion, selectivity and reactor yield with respect to;

a. toluene feed
b. hydrogen feed
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 Review on Chemical Reactors
Solution:
Calculation based on Toluene

Toluene conversion = (toluene consumed) / (toluene feed) = (372-93) / 372 = 0.75

Stoichiometric factor : 1 mol toluene to produce 1 mol benzene

Benzene selectivity from Toluene = benzene produced / toluene consumed = [ (282 – 13) / (372 – 93) ] x 1 = 0.96

Reactor yield from Toluene = [benzene produced / toluene fed to reactor] X Stoichiometric Factor (Benzene)
= [ (282 – 13) / (372) ] x 1 = 0.72

Calculation based on Hydrogen

Hydrogen conversion = (hydrogen consumed) / (hydrogen feed) = (1858 - 583) / 1858 = 0.15

Stoichiometric factor : 1 mol hydrogen to produce 1 mol benzene

Benzene selectivity from Toluene = benzene produced / hydrogen consumed = [ (282 – 13) / (1858 – 1583) ] x 1 = 0.98

Reactor yield from Toluene = [benzene produced / hydrogen fed to reactor] X Stoichiometric Factor (Benzene)
= [ (282 – 13) / (1858) ] x 1 = 0.14
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 Review on Chemical Reactors
During the conceptual design of a chemical process, among the related decisions that have to be made
concerning reactor ;

Reactor Type and/or Network Operating Conditions

 Temperature
 Pressure
CSTR OR BATCH  Concentration
CSTR
 Inert
PLUG FLOW
 Catalyst
PLUG FLOW RECYCLE REACTOR

RECYCLE REACTOR PLUG FLOW

HOW DO WE DECIDE ?
REACTOR VOLUME
RECYCLE REACTOR
AND CSTR

ORIENTATION

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Synthesis of Reactor/Reactor Network – Heuristic Approach

DESIGN PROCEDURE FOR REACTOR SELECTION

1. Gather important information required on the reaction needed for the process. What information are needed ?

Info. 1 Reaction path selected for the production of the desired products.
Q. How do we select the most desirable reaction path ?
Economic Potential !

Info. 2 Types of reaction system involved

Single Reaction
Feed (s) -----> Product + Byproduct (s)
Multiple Reactions in parallel
producing byproducts
Feed (s) -----> Product + Byproduct (s)
Feed (s) -----> Byproduct (s)
Polymerisation Reaction
Multiple Reactions in series
producing byproducts
Feed (s) -----> Product + Byproduct (s)
Product -----> Byproduct (s)
Mixed Parallel and Series Reactions
producing byproducts
Feed (s) -----> Product + Byproduct (s)
Feed (s) -----> Byproduct (s)
Product -----> Byproduct (s)

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Synthesis of Reactor/Reactor Network – Heuristic Approach
2. Select the reactor (network) based on the gathered information.

Single Reaction..... Feed(s) -------> Product + Byproduct(s) e.g.: Dehydrogenation of Isopropyl Alcohol to produce Acetone

formation of product & byproduct is directly related !

What is our aim here when selecting the type of reactor (network) ?

For a specified reactor conversion, try to minimise the reactor volume !

Question: What type of reactor should we select ?

PLUG FLOW
CSTR

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Synthesis of Reactor/Reactor Network – Heuristic Approach
Multiple Reactions in parallel producing byproducts

Feed -------> Product e.g.: Production of Phtalic Anhydride from o-xylene. Competing reaction is the
formation of maleic anhydride.
Feed -------> Byproduct

formation of product & byproduct is by 2 different mechanisms

What is our aim here when selecting the type of reactor (network) ?

Minimise byproduct formation / maximise product formation

Maximise Selectivity !
a1
Feed ------> Product (s) Rxn 1 : r1 = k1 Cfeed
a2
Feed ------> Byproduct (s) Rxn 2 : r2 = k2 Cfeed
r2 k2 a2 – a1
important = Cfeed Ratio of secondary to primary reaction
r1 k1
Point for Discussion
What can you say about getting maximum selectivity and relate that to
conversion !

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Synthesis of Reactor/Reactor Network – Heuristic Approach

r2 k2 a2 - a1
Ratio of secondary to primary reaction
= Cfeed
r1 k1
For a2 < a1 For a2 > a1
selectivity increases as selectivity decreases as
conversion increases conversion increases

Go for maximum possible conversion ! Go for minimum possible conversion !

PLUG FLOW PLUG FLOW

CSTR
CSTR

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Synthesis of Reactor/Reactor Network – Heuristic Approach
Consider more reactions system below:

Feed 1 + Feed 2 -------> Product

Feed 1 + Feed 2 -------> Byproduct (s)

What is our aim here when selecting the type of reactor (network) ?

Minimise byproduct formation / maximise product formation

Maximise Selectivity !
a1 b1
Feed ------> Product (s) Rxn 1 : r1 = k1 Cfeed1 Cfeed2
a2 b2
Feed ------> Byproduct (s) Rxn 2 : r = k2 Cfeed1 Cfeed2
2

r2 k2 a2 - a1 b2 -b1 Ratio of secondary to primary reaction

important = Cfeed1 Cfeed2
r1 k1

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 Synthesis of Reactor/Reactor Network – Heuristic Approach

r2 k2 a2 - a1 b2 -b1 Ratio of secondary to primary reaction

= Cfeed1 Cfeed2
r1 k1

For a2 < a1 For a2 > a1

i. b2 > b1 i. b2 > b1

REACTANT 2 REACTANT 2
REACTANT 2
REACTANT 1

REACTANT 1
REACTANT 1
SEMI PLUG FLOW CSTR

SEMI BATCH

ii. b2 < b1
REACTANT 1 REACTANT 1
ii. b2 < b1

REACTANT 2
REACTANT 2
PLUG FLOW
SEMI PLUG FLOW

SEMI BATCH

Can you explain why ?

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 Synthesis of Reactor/Reactor Network – Heuristic Approach

Multiple Reactions in series producing byproducts

Feed (s) -------> Product e.g: Production of Phtalic Anhydride from o-xylene followed by production of CO2.
Product -------> Byproduct (s)

formation of byproduct is influenced by product concentration

What is our aim here when selecting the type of reactor (network) ?

Minimise byproduct formation / maximise product formation

Maximise Selectivity !
a1
Feed ------> Product (s) Rxn 1 : r1 = k1 Cfeed
a2
Product ------> Byproduct (s) Rxn 2 : r2 = k2 Cproduct

Have to build the concentration of the product to

an optimum level before removing it from Control of residence time is important !
reactor to avoid formation of byproducts. Therefore, plug flow is selected.

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Synthesis of Reactor/Reactor Network – Heuristic Approach

Mixed Parallel & Series Reactions producing byproducts.....

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

Feed (s) -------> Byproduct (s) Here, we should also be attempting to select reactor system that
maximises the selectivity !
Product -------> Byproduct (s)

a1
Feed (s) ------> Product (s) Rxn 1 : r1 = k1 Cfeed
a2
Feed (s) ------> Byproduct (s) Rxn 2 : r2 = k2 Cfeed
a3
Product ------> Byproduct (s) Rxn 3 : r3 = k3 Cproduct

A Recall from what we have learned earlier…

Point for discussion
For parallel byproduct reaction, favors
What if we have a case
i. plug flow if a1 > a2 where the reactions are
ii. CSTR if a1 < a2 mixed and the order of
For series byproduct reaction, plug flow favors. a1 < a2 ?

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Synthesis of Reactor/Reactor Network – Heuristic Approach

PLUG FLOW

CSTR

Neither Plug Flow nor CSTR

Some level of mixing between them !
Question
How can we have such configuration ?

OR OR

CSTR PLUG FLOW

CSTR
PLUG FLOW REACTOR WITH RECYCLE OR

CSTR

PLUG FLOW

CSTR

CSTR
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 CONCLUSIONS

We have looked at the followings;

• Types of Reaction System : Parallel, Series Parallel, Polymerisation etc.

• Selection of Suitable Reactor for a Specified Reaction System :
• Plug flow
• CSTR
• Semi Plug flow

Together, they form the overall guidelines for deciding the conceptual design
for the reactor/reactor network.

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