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CDB 3044

PROCESS PLANT DESIGN

Conceptual Process Design - Synthesis of Reaction System (II)


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Learning Outcomes

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. Analyze the mathematical approaches for reactor network

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Polymerization Reaction
Polymers are characterized by the distribution of molecular weight.

2 broad types of reaction

1. Reactions with Termination steps


e.g. polymerization of Vinyl Chloride

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


initiator vinyl chloride free radical
vinyl chloride
CH3 or
OH propagates

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


Question ?
leading to How do we select suitable
type of reactor for such
R - (CH2 - CHCl)n - CH2 - CHCl Polymers reaction ?
Reaction terminated by
the joining of these molecules

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Polymerization Reaction
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 Reaction terminated by


Polymers
the joining of these molecules

Best to choose CSTR.


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 CSTR
concentration thus harder for termination steps to take place resulting
in longer chain molecule.

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Polymerization Reaction
2. Reactions without Termination Step.

e.g. 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

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Example on Reactor Selection
Question: Given the following reaction systems to produce product C, select a
suitable reactor for the system.

A+BC rC = k1 CA0.5 CB2

CD rD = k2 CC2 Mixture of series and parallel reactions


A+BD rD = k3 CA CB

Analysing the parallel reaction:


r3 k3 1-0.5 1-2
A+BC rC = k1 CA 0.5 CB2 = CA CB
r1 k1
A+BD rD = k3 CA CB r3 k3
CA
0.5
CB
-1
=
r1 k1

What reactor configuration should be selected?

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Example on Reactor Selection (Cont.)
A
r3 k3 1-0.5 1-2
= CA CB
r1 k1
r3 k3 0.5 -1
= CA CB B
r1 k1
Semi CSTR

OR
Analyzing the series reaction:
A + B  C rC = k1 CA0.5 CB2
REACTANT A

CD rD = k2 CC2

REACTANT B
Control of residence time is important. SEMI PLUG FLOW
Therefore, choose plug flow.

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Reactor Operating Parameter
The choice of the reactor is made based on the most appropriate concentration profile as the reaction progresses.
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.


a A + b B  c C + d D
Pressure Effect

The extent of reaction which can be calculated using Gibbs Free Energy. 𝑑𝐺 = 𝑉 𝑑𝑃

∆𝐺 0 = −𝑅𝑇 ln 𝐾𝑎 where

∅𝐶 𝑐 . ∅𝐷 𝑑 𝑝𝐶 𝑐 . 𝑝𝐷 𝑑
𝐾𝑎 =
∅𝐴 𝑎 . ∅𝐵 𝑏 𝑝𝐴 𝑎 . 𝑝𝐵 𝑏 For gaseous reaction

𝛾𝐶 𝑐 . 𝛾𝐷 𝑑 𝑥𝐶 𝑐 . 𝑥𝐷 𝑑
𝐾𝑎 =
𝛾𝐴 𝑎 . 𝛾𝐵 𝑏 𝑥𝐴 𝑎 . 𝑥𝐵 𝑏 For liquid reaction

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Example
Question: Given reaction below at 1 bar, 300 K to produce Ammonia NH3.
Feed is according to the stoichiometric ratio.
3 H2 + N2  2 NH3
0 𝑘𝐽
Given the data for Std. Free Energy of Formation 𝐺ҧ300 ( )
𝑘𝑚𝑜𝑙
Assume ideal gas law…
H2 0
N2 0
a. Determine Ka (equilibrium constant)
NH3 -16.223
∆𝐺 0
ln 𝐾𝑎 =
−𝑅𝑇 H2 N2 NH3
−(−2 16,223 − 0 − 0 )
ln 𝐾𝑎 = = 13.008
8.314 × 300 Initial moles 3 1 0
𝐾𝑎 = 4.4597 × 105 Equilibrium moles 3-3X 1-X 2X
𝑝𝑁𝐻3 2 𝑦𝑁𝐻3 2 Total moles at equilibrium = 4 – 2X
𝐾𝑎 = 3 = 3 𝑃−2
𝑝𝐻2 .𝑝𝑁2 𝑦𝐻2 .𝑦𝑁2

Mole Fraction 3-3X 1-X 2X

4-2X 4-2X 4-2X

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Example
Question: 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
b. Composition of the reaction products at equilibrium
3-3X 1-X 2X
𝑝𝑁𝐻3 2 𝑦𝑁𝐻3 2 Mole Fraction
𝐾𝑎 = = 𝑃−2 4-2X 4-2X 4-2X
𝑝𝐻2 3 .𝑝𝑁2 𝑦𝐻2 3 .𝑦𝑁2

𝑦𝑁𝐻3 2 −2
16𝑋 2 2 − 𝑋 2
𝐾𝑎 = 𝑃 = for P = 1 bar
𝑦𝐻2 3 . 𝑦𝑁2 27 1 − 𝑋 4

X = 0.97 bar

Therefore, the composition at equilibrium is ;

H2 [3 – 3 (0.97)] / [4 – 2 (0.97)] = 0.0437


N2 [1 – (0.97)] / [4 – 2 (0.97)] = 0.0146
NH3 [2 (0.97) / [4 – 2 (0.97)] = 0.9418

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Reactor Operating Parameter
Besides looking at the reaction system, the other aspects governing chemical reaction which have to be
considered are;
2. Reaction Equilibrium for reversible reaction. a A + b B  c C + d D

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

𝑑 ∆𝐺 0 ∆𝐻0 𝑑 ln 𝐾𝑎
=− 2 = from ∆𝐺 0 = −𝑅𝑇 ln 𝐾𝑎
𝑑𝑇 𝑇 𝑃
𝑇 𝑑𝑇
Integrate the above relation ;
𝑘𝑎2 ∆𝐻0 1 1
𝑙𝑛 =− −
𝑘𝑎1 𝑅 𝑇2 𝑇1
The effect of temperature on reaction equilibrium could be determined since the std. heat of reaction is available in thermodynamics data.

∆𝐻0 = 𝑐𝐻𝐶0 + 𝑑𝐻𝐷0 − 𝑎𝐻𝐴0 − 𝑏𝐻𝐵0

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

3. Rate of Reaction - Temperature Effect a A + b B  c C + d D

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

𝐸
𝑘 = 𝑘0 𝑒 𝑅𝑇

Expanding the above equation:


𝑘2 𝐸 1 1
𝑙𝑛 = − E is the activation energy.
𝑘1 𝑅 𝑇1 𝑇2

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

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Design Procedure for Reactor Operating Parameter
Concentration of Reactants

Some possibilities to consider

EXCESS OF ONE REACTANTS ADDITION OF INERTS


This can force the reaction of a selected This can favor reaction to proceed
component to complete due to certain towards favorable direction.
reason.

eg. C2H4 + Cl2 ---> C2H4Cl2 eg. Feed <==> Prod1 + Prod2

Cl2 is difficult to separate. Add excess of C2H4 causes Reaction causes an increase in no. of moles. Adding
the completion reaction of Cl2 inert cause reduction in no. of moles/vol.
Therefore, reaction proceeds to produce more products.

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Design Procedure for Reactor Operating Parameter
Concentration of Reactants

Some possibilities to consider

REMOVAL OF PRODUCT RECYCLE UNWANTED BYPRODUCTS


This can get the reaction to proceed to This can suppress the formation
the favorable direction. of more unwanted by-products.

eg. 2SO2 + O2  2SO3 eg. Feed1 + Feed2  Product


Feed1 + Feed2  Byproduct Rxn 2
Intermediate removal of Sulfur trioxide will make
the reaction towards producing more products. But
how?
H2O H2O

R A R A

Recycling byproduct will suppress


absorption absorption reaction 2 thus avoiding waste of feed material

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Design Procedure for Reactor Operating Parameter
Concentration of Reactants

Multiple reactions in parallel producing byproducts

a1 b1
Feed1 + Feed2 ------> Product (s) Rxn 1 : r1 = k1 Cfeed1 Cfeed2
a2 b2
Feed1 + Feed2 ------> Byproduct (s) Rxn 2 : r2 = k2 Cfeed1 Cfeed2

r2 k2 a2 -a1 b2 -b1
Ratio of secondary to primary reaction = Cfeed1 Cfeed2
r1 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.

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Design Procedure for Reactor Operating Parameter
Concentration of Reactants
Multiple reaction in series producing byproducts
a1
Feed(s) -------> Product Rxn 1 : r1 = k1 Cfeed
a2
Product -------> Byproduct(s) Rxn 2 : r2 = k2 Cproduct

Formation of byproducts is minimized by keeping the product composition low in the reactor.

Options that can be considered :

 Use of 3rd component which does not participate in the reaction to decrease byproducts production.

 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.

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Design Procedure for Reactor Operating Parameter
Concentration of Reactants
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
a2
Feed(s) ------> Byproduct(s) Rxn 2 : r2 = k2 Cfeed
a3
Product ------> Byproduct(s) Rxn 3 : r3 = k3 Cproduct

Options that can be considered :

 The use of excess 3rd component which does not involve in reaction to decrease byproduct production.
It can suppress the byproduct formation by keeping product composition low.

 Recycling of byproducts if the reaction is reversible can assist in minimizing byproduct formation.

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Design Procedure for Reactor Operating Parameter
Temperature

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 oC 550 oC

Carbon Steel (grade 70) 1190 970 170


Stainless Steel (Type 302) 1290 1290 430

A decision to operate above 400 oC 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 o C to 260 o C requiring special heating/cooling
media, has to be justified. Within this range, normal steam and cooling water could be utilized easily.

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Design Procedure for Reactor Operating Parameter
Temperature (T)

How do we decide ?

SINGLE REACTION MULTIPLE REACTIONS

Endothermic Rxn For Parallel/Series Reaction


Set T as high as possible A ---> B ---> C B product
Good for rate of reaction k1 k2

If k1 increases more than k2 with respect to T, then go for as


So what is the limit ? highest T as possible.
Exothermic Rxn
if k2 increase more than k1 with respect to T, then go for as
Set T low to take advantage on lowest T as possible. Careful, as need to compromise!
conversion in a reversible reaction.
The main issue is how to control T effectively.
Not good for rate of reaction Can you suggest a number of ways to do that?
Need to compromise !
So what is the compromise ?

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Design Procedure for Reactor Operating Parameter
Pressure

There are economic advantages associated with operating equipment at higher pressure when gases are
present i.e., decrease in gas volume. This tends 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 are 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

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Design Procedure for Reactor Operating Parameter
Pressure

For liquid phase reaction, pressure is known to have little effect. Why?

For vapor phase reaction:


SINGLE REACTION
MULTIPLE REACTIONS
Decrease in number of moles The same general guideline can be used but
Pressure decreases as reactant/s consideration has to be given when having
were converted to products competing reactions producing byproducts.
Increase pressure to take advantage.
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.

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Design Procedure for Reactor Operating Parameter
Phase of Reaction Mixture

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

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

 Higher density thus higher concentration


per volume size
Smaller Reactor Volume
 Rate of mass/Heat transfer
Gas phase might have better transfer of mass

Liquid phase might have better transfer of heat

 Safety consideration

Not so much of an important criteria !

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Design Procedure for Reactor Operating Parameter
Catalyst Selection
Function of Catalyst :

To increase the rate of reaction without changes in quantity and composition at the end of reaction.

Homogenous Catalyst Heterogeneous Catalyst

It may modify reaction mechanism by participating  Catalyst differs in phase from reacting species.
in the reaction but is regenerated back in the
subsequent step.  Often, it is solid.
e.g. production of ketene from acetic acid
 Reacting species diffuse to surface of catalyst and are adsorbed.
CH3COOH ----> CH2=C=O + H2O Reaction takes place and products then desorbed and diffused
uses triethyl phospate as a catalyst. back to bulk gas/liquid.

 Effective surface area on catalyst which depends on catalyst


Problem : possible loss of catalyst due to imperfect
porosity is an important consideration.
separation to recover catalyst.

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Design Procedure for Reactor Operating Parameter
Example (Text by Smith R. pg. 80):
Given the reaction below for the production of monoethanolamine;

Ethylene oxide + ammonia  monoethanolamine

Monoethanolamine + ethylene oxide  diethanolamine Side reaction

Diethanolamine + ethylene oxide  triethanolamine Side reaction

Select a reactor that will maximize 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.

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Design Procedure for Reactor Operating Parameter
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

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Synthesis of Reactor Network
Recall the following information

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
Operating Conditions
 TEMPERATURE
 PRESSURE
 CONCENTRATION
CSTR OR BATCH
CSTR
 INERT
 CATALYST

PLUG FLOW
PLUG FLOW RECYCLE REACTOR

RECYCLE REACTOR
?
PLUG FLOW

REACTOR VOLUME HOW DO WE


RECYCLE REACTOR
AND ORIENTATION CSTR DECIDE ?

We tackle this using heuristic approach !


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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, requires complex reactor - network of reactor !

A  B
A + B  C  D exotherm. rxn
B  C
A + C  E endotherm. rxn
Simple plug flow reactor B + D  F endotherm. rxn

D is the product !
Could be:

 Flow Pattern
How can we derive such configuration or network just from the heuristic guideline ?
 Mixing Location
 Heating & Cooling The method that can deliver this will need extensive mathematics and programming.
- Mathematical Programming Approach.

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Synthesis of Reactor Network
Mathematical Programming Approach
But how do we go about doing this ?

Recall the key information required when designing reactor:

Reaction Chemistry Reaction Kinetics


But for complex reaction chemistry, since mathematical programming
For simple reaction chemistry, selection of reactor can be done
approach is to be adopted, detailed reaction kinetics now become important.
using the heuristic guideline even without the reaction kinetics.

Still the important parameters that decide the reactor network are Conversion and 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 optimize it in order to produce the optimal solution.

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Synthesis of Reactor Network
Mathematical Programming Approach
SUGGESTED PROCEDURE

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:
Variables 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.

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Synthesis of Reactor Network
Mathematical Programming Approach
To briefly understand how it works,
Consider a reaction: A  B  C

C
A B

Time

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Synthesis of Reactor Network
Mathematical Programming Approach

A BC
CB
F
G

CSTR
PLUG FLOW

H
CA

For a PFR with variable residence time and fixed feed CA0 and CB0, one can solve the ordinary differential equations from the feed
point :

dCA / dt = rA
dCB / dCA = rB / rA From this differential equation we can plot the trajectory for HEGF.
dCB / dt = rB

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Synthesis of Reactor Network
Mathematical Programming Approach

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

CB
F
G

CSTR

PLUG FLOW
E

H
CA
For a CSTR, the path from the feed can be generated using the equations:

CA - CA0 = t rA CA - CAo
= rA / rB
CB - CBo = t rB CB - CB0 From this equation 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.

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Synthesis of Reactor Network
Mathematical Programming Approach
How do we plot the attainable region ?
CB
Plot the attainable region using reaction/rate vectors. The F
eqn. for the vectors are obtained from the plug flow and/or G
CSTR trajectory as shown earlier.

CSTR

PLUG
FLOW
E
H
dCB / dCA = rB / rA Plug Flow
CA - CAo CA
= rA / rB CSTR
CB - CBo

Example 13.3 page 443 : Systematic Methods of Chemical Process Design by Biegler, Grossman & Westerberg, illustrates the application of the method !
.

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Synthesis of Reactor Network
Mathematical Programming Approach
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 reduce the number of
options that have to be dealt by the mathematical programming during optimization.

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
Operating Conditions
 TEMPERATURE
 PRESSURE
 CONCENTRATION
CSTR OR BATCH
CSTR
 INERT
 CATALYST

PLUG FLOW
PLUG FLOW RECYCLE REACTOR

RECYCLE REACTOR
?
PLUG FLOW

REACTOR VOLUME HOW DO WE


RECYCLE REACTOR
AND ORIENTATION CSTR DECIDE ?

is made simpler !

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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

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