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Polymerization Reaction
Polymers are characterized by the distribution of molecular weight.
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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.
leading to
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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
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.
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.
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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
CD 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;
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
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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
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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
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.
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;
The effect of temperature on rate of reaction can be computed from the Arrhenius equation.
𝐸
𝑘 = 𝑘0 𝑒 𝑅𝑇
Generally, the higher the temperature, the higher is the reaction rate.
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Design Procedure for Reactor Operating Parameter
Concentration of Reactants
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
R A R A
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Design Procedure for Reactor Operating Parameter
Concentration of Reactants
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.
Use of 3rd component which does not participate in the reaction to decrease byproducts production.
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Design Procedure for Reactor Operating Parameter
Concentration of Reactants
Mixed parallel and series reactions producing byproducts
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
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
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 ?
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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.
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Design Procedure for Reactor Operating Parameter
Pressure
For liquid phase reaction, pressure is known to have little effect. Why?
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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 !
Safety consideration
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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.
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.
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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;
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;
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.
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
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 ?
Still the important parameters that decide the reactor network are Conversion and Selectivity.
Selectivity normally becomes the more dominant one.
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.
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 BC
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
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.
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
is made simpler !
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Conclusions
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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