Chapter 6

BITS, PILANI K. K.
BIRLA GOA CAMPUS
MULTIPLE REACTIONS Chapter 6

PROF. SRINIVAS KRISHNASWAMY ASSOCIATE PROF. & HEAD OF DEPARTMENT DEPARTMENT OF CHEMICAL ENGINEERING BITS PILANI, K. K. BIRLA GOA CAMPUS
Introduction
After this chapter you will be able to focus on reactor selection and mole balances for multiple reactions Seldom does 1 reaction occur in a reactor Multiple reactions will occur (some desired / some undesired) Economic success of a plant depends on minimizing undesired side reactions
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How we will go about it?

Describe basic types of multiple reactions Define Selectivity and how it can be used to minimize unwanted side reactions Choice of operating conditions and reactor type
Develop an algorithm to solve reaction engineering problems when multiple reactions are involved
Types of reactions
SERIES REACTIONS (CONSECUTIVE REACTIONS)
Reaction of ethylene oxide with ammonia to form mono, di and tri-ethanol amine
PARALLEL REACTIONS (COMPETING REACTIONS)
Two different pathways to form different products
Oxidation of ethylene to ethylene oxide

Types of reactions
COMPLEX REACTIONS (CONSECUTIVE REACTIONS)
Butadiene butadiene)
from
ethanol
(ethylene,
acetaldehyde,
INDEPENDENT REACTIONS
Crude oil to Gasoline
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BITS, PILANI K. K. BIRLA GOA CAMPUS
Desired and Undesired Reactions

A D (kd) A U (ku)
ADU
Minimize the formation of U and maximize U (objective)
ECONOMIC INCENTIVE
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Possible reactions
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Selectivity and Yield

Selectivity: Indication of preference of one product over another
INSTANTANEOUS
OVERALL
For batch reactor it will be in terms of number of moles (Can we compare it for a CSTR?)

Yield: Ratio of the reaction rate of a given product to the reaction rate of the key reactant A
INSTANTANEOUS
OVERALL
For batch reactor it will be in terms of number of moles (Can we compare it for a CSTR)
SELECTIVITY & CONVERSION NOT THE BEST OF FRIENDS!!

Problem (Product Distribution)
Solution
Solution
Solution
Solution
Solution
Problem (Good operating conditions)
Solution
Solution
Solution
Solution
Problem (Best Operating conditions)
Based on previous example
Solution
Qualitative assessment
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Contacting patterns
Contacting patterns
Problem
Solution
SOLUTION
Solution

desired product , rD=k1CA2CB
undesired product , rU=k2CACB
Selectivity parameter
Run at high concentration of A. Use PFR.
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Parallel reactions
A D (kd) A U (ku)
desired product , rD=kDCA1 undesired product , rU=kUCA2
rA = rD + rU (1 and 2 are positive reaction orders)
Objective: rD and ru
= (kD/kU)CA1 - 2
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Parallel reactions
Case 1: 1 > 2 Case 1: 1 < 2 Should the reaction be run at high or low temperatures? SD/U~ kD / kU = (AD / AU)e-[(ED Case 1: ED > EU Case 1: ED < EU
EU) / RT]
Parallel reactions
desired product , rD=k1CA1CB1
undesired product , rU=k2CA2CB2
= (k1/k2)CA1 - 2CB1-2
Depends on whether 1 - 2 & 1-2 are positive and negative
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DIY (Contacting Schemes)

The desired liquid phase reaction
A + B R + T (k1) dCR/dt = dCT/dt = k1CACB0.5 A + B S + U (k1) dCS/dt = dCU/dt = k1CA0.5 CB1.8

From the standpoint of favourable product distribution, order the contacting schemes from most desirable to least desirable
Parallel reactions (Problem)

Determine the instantaneous selectivity, SD/U, for the liquid phase reactions
Sketch the selectivity as a function of the concentration of A. Is there an optimum and if so what is it?
Parallel reactions (Solution)

Write the equation for selectivity
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Parallel reactions (What else?)

Selectivity can be calculated
We can now calculate maximize selectivity reactor volume to
We can estimate the temperature at which we can operate the CSTR

We can estimate conversion Can we increase conversion of desired product?
Irreversible First Order Reactions in series
Rate Equations
Qualitative discussion- Product Distribution
Qualitative discussion- Product Distribution (Series Reactions)
Contacting Patterns
Contacting Patterns
Series reactions
Here the important variable is space time for a flow reactor and real time for a batch reactor Case 1: R1 faster than R2 Case 1: R1 slower than R2
Series reactions
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Series reactions
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Series reactions
Which gives
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Series reactions
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Series reactions
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Series reactions
Reaction (1) Reaction (2)
Species A:
Species B:
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Series reactions
Dividing by IF. we see we arrive back at Equation 1
Now integrating Equation (2)
Differentiating the RHS of Equation (2)
Evaluating the constant of integration K1
when t = 0 then
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Series reactions
When do we stop the reaction to maximize B?
What is Xopt?
Series reactions (Quantitative treatment PFR)
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Series reactions (Quantitative treatment)
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Series reactions (Quantitative treatment MFR)
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Reaction Selection criteria

Selectivity Yield
Temperature Control
Safety Cost
Finding the Selectivity

For the elementary reaction,
with k1=0.1 s-1 and k2=0.2 s-1 with CAO= 2 mol/dm3. Plot the concentration of B and selectivity of B to C as a function of space time in a CSTR.
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Species Balance on A & B
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Species Balance on C
The space time, * is the minimum value of V (i.e. *) at which there is an acceptable molar flow rate of the desired product B from the CSTR.
Algorithm for Multiple Reactions
FOLLOW THE ALGORITHM
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Mole balance
Reactor Type
Batch Semi-batch (B added to A) CSTR
Gas Phase
Liquid Phase
PFR
PBR
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Application of the algorithm

Example: Liquid Phase Reaction
Case 1: PFR (Mole balance for A, B, C and D)
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Write the rate laws
A+2B-->C
3C+2A-->D
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SPECIES A
SPECIES B
SPECIES C
SPECIES D
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STOICHIOMETERY
SPECIES A SPECIES B
SPECIES C SPECIES D

TIME TO USE POLYMATH k1A=0.5
k2C=2.0
at t=0: V=0, CAO=4, CBO=4, CCO=0, CDO=0
THINGS GETTING OUT OF HAND

April 16, 2013 BITS, PILANI K. K. BIRLA GOA CAMPUS
Vf=5 dm3
84
Polymath Solution - 1
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Case 2: CSTR : Liquid Phase
SPECIES A SPECIES B
SPECIES C SPECIES D
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We will specify V, CAo, CBo along with the specific reaction rates kij. This formulation leaves us with four equations and four unknowns (CA, CB, CC, and CD).
Nonlinear equations [1] f(Ca) = vo*(Cao-Ca)V*(k1a*Ca*Cb^2+2/3*k2c*Ca^2*Cc^3) = 0 [2] f(Cb) = vo*(Cbo-Cb)-V*(2*k1a*Ca*Cb^2) = 0 [3] f(Cc) = -vo*Cc+V*(k1a*Ca*Cb^2-k2c*Ca^2*Cc^3) = 0 [4] f(Cd) = -vo*Cd+V*(k2c*Ca^2*Cc^3)/3 = 0 Explicit equations [1] Cao = 4 [2] Cbo = 4 [3] k1a = 0.5 [4] k2c = 2 [5] V = 5 [6] vo = 5
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Variable Ca
Value 1.9839539
Cb Cc Cd
1.1900914 0.4883166 0.3055459
88

Case 2: Semi Batch: Liquid Phase
SPECIES A SPECIES B
SPECIES C SPECIES D
V=VO+vOt
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Multiple reactions: Gas Phase (PFR)
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SPECIES A
SPECIES B SPECIES C rB = r1B
rC = r1C + r2C rD = r2D

BITS, PILANI K. K. BIRLA GOA CAMPUS 92
SPECIES D
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RELATIVE RATES
r2C = - k2CCA2CC3
r1A = - k1ACACB2
Reaction (1)
A + 2B -> C r1A/-1 = r1B/-2 = r1c/1 r1B = 2r1A r1C = -r1A
Reaction (2)
2A + 3B -> D r2A/-2 = r2C/-3 = r2D/1
r2A = (2/3)r2C
r2D = -(1/3)r2C
Species A
Species B Species C Species D
(1)
(2) (3) (4)
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Stoichiometry
Combine Species A Species B Species C
Species D
Polymath Solution
Initial Conditions
Use the Polymath ordinary differential equation solver
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Multiple reactions: Gas Phase (CSTR)

All equations apply as do initial conditions
A: B:
C:
D:
Total: FT = FA + FB + FC + FD
Use the Polymath nonlinear equation solver

Practice Problem
Write the net rates of formation for A, B, C and D (Reactions are elementary)
In a CSTR for gas phase, all the equations mentioned in last few slides apply.
Objective Assessment of Chapter

Define different types of selectively and yield Choose the appropriate reactor and reaction system that would maximize the selectivity of the desired product given the rate laws for all the reactions occurring in the system Describe the algorithm used to design reactors with multiple reactions Apply the CRE algorithm to size reactors in order to maximize the selectivity and to determine the species concentrations in a batch reactor, a semi-batch reactor, a CSTR, a PFR, and a PBR, in systems with multiple reactions The only way of finding the limits of the possible is by going beyond them into the impossible. Arthur C. Clarke

Chapter 6

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Chapter 6

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BITS, PILANI K. K.

BIRLA GOA CAMPUS

MULTIPLE REACTIONS Chapter 6

How we will go about it?

Oxidation of ethylene to ethylene oxide

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

Desired and Undesired Reactions

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

Selectivity and Yield

Selectivity and Yield

SELECTIVITY & CONVERSION NOT THE BEST OF FRIENDS!!

Selectivity and Yield

Selectivity and Yield

Selectivity and Yield

Selectivity and Yield

Selectivity and Yield

Selectivity and Yield

Problem (Product Distribution)

Problem (Good operating conditions)

Problem (Best Operating conditions)

Based on previous example

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

Selectivity and Yield

undesired product , rU=k2CACB

Run at high concentration of A. Use PFR.

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

rA = rD + rU (1 and 2 are positive reaction orders)

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

Depends on whether 1 - 2 & 1-2 are positive and negative

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

DIY (Contacting Schemes)

A + B R + T (k1) dCR/dt = dCT/dt = k1CACB0.5 A + B S + U (k1) dCS/dt = dCU/dt = k1CA0.5 CB1.8

Parallel reactions (Problem)

Parallel reactions (Solution)

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

Parallel reactions (What else?)

We can estimate the temperature at which we can operate the CSTR

Irreversible First Order Reactions in series

Qualitative discussion- Product Distribution

Qualitative discussion- Product Distribution (Series Reactions)

Qualitative discussion- Product Distribution

Qualitative discussion- Product Distribution

Qualitative discussion- Product Distribution

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS

April 16, 2013

BITS, PILANI K. K. BIRLA GOA CAMPUS