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Chapter 6 Summary Notes
11-14 minutes
6. Multiple Reactions*
Topics
1. Types of Multiple Reactions Selectivity and Yield
2. Parallel Reactions
3. Reactions in Series
4. Algorithm for Complex Reactions
5. Applications of Algorithm
1. Types of Multiple Reactions Selectivity and Yield top
Types of Multiple Reactions
6.1 What type of reaction is taking place?
Selectivity and Yield (Section 6.1)
There are two types of selectivity and yield: Instantaneous and Overall.
Instantaneous Overall
Selectivity
Yield
desired product , rD=k1CA2CB
undesired product , rU=k2CACB
Example:
To maximize the selectivity of D with respect to U run at high concentration of A and use PFR
2. Parallel Reactions top
The net rate of disappearance of A
Instantaneous selectivity
If α > β use high concentration of A. Use PFR.
If α < β use low concentration of A. Use CSTR.
6.2 Maximizing the Selectivity - Parallel Reactions
3. Series Reactions (p. 283) top
Example: Series Reaction in a batch reactor
This series reaction could also be written as
Reaction (1) : -r1A=k1CA
Reaction (2) : -r2B=k2CB
Mole Balance on every species
Species A:
Combined mole balance and rate law for a control volume batch
reactor.
Net Rate of Reaction of A
rA=r1A+0
Rate Law
r1A=-k1ACA
Relative Rates
r1B=-r1A
Integrating with CA=CA0 at t=0 and then rearranging
Mole Balance
Species B:
Net Rate of Reaction of B
Rate Law
r2B=-k2CB
Relative Rates
Combine
Using the integrating factor, i.f.:
Evaluate
at t = 0, CB = 0
When should you stop the reaction to obtain the maximum amount of B? Let's see.
Optimization of the Desired Product B
Then
Species C CC = CA0 - CB - CA
And
6.3 Finding the Selectivity
in a CSTR
6.4 Concentration-Time Trajectories
Schemes for maximizing the selectivity for Van Der Vusse Kinetics
Can be found at the following web site http://www.wits.ac.za/centres/comps/AR/index.htm
4. Algorithm for Complex Reactions top
Mole Balances
Reactor Type Gas Phase Liquid Phase
Batch
Semibatch
CSTR
PFR
PBR
Rates
NOTE: The reaction rates in the above mole balances are net rates.
The new things for multiple reactions that build on Figure 4-11 and Table 4-6 are
1. Number every reaction
2. Rate Law for every reaction
3. Relative Rates for every reaction
4. Net Rates of Reaction
1. Number every reaction
2. Rate Laws for every reaction
3. Relative Rates for each reaction
For a given reaction i
4. Net Rate of Formation for Species A that appears in N reactions,
Stoichiometry
NOTE: We could use the gas phase mole balance for liquids and then just express the concentration as
Flow CA = FA/υ0
Batch CA = NA/V0
6.5 Writing Net Rates of Formation
5. Applications of Algorithm top
NOTE: The specific reaction rate k1A is
(1)
defined with respect to species A.
NOTE: The specific reaction rate k2C is
(2)
defined with respect to species C.
These reactions will be used in the following 5 examples
• Liquid Phase PFR
• Liquid Phase CSTR
• Gas Phase PFR no ΔT
• Gas Phase Membrane Reactor with ΔT
• Liquid Phase Semibatch Reactor
Example A: Liquid Phase PFR
The complex liquid phase reactions follow elementary rate laws
(1) A + 2B → C -r1A = k1ACACB2
(2) 2A + 3C → D -r2C = k2CCA2CB3
and take place in a PFR. The feed is equal molar in A and B with FA0 = 200 mol/min and the volumetric
flow rate is 100 dm3/min. The reaction volume is 50 dm3 and the rate constants are
Plot FA, FB, FC, FD and SC/D as a function of V
6.6 Multiple Reactions - Sketch what you think the profile will look like a priori
Solution
Liquid PFR
Mole Balances
Net Rates
Rate Laws
Relative Rates
Selectivity
If one were to write SC/D = FC/FD in the Polymath program, Polymath would not execute
because at V = 0, FC = 0 resulting in an undefined volume (infinity) at V = 0. To get around this
problem we start the calculation 10-4 dm3 from the reactor entrance where FD will note be zero
and use the following IF statement.
Stoichiometry
Parameters
Would you like to see the results for Example A
Would you like to run for Example A
Example B: Liquid Phase CSTR
Same reactions, rate laws, and rate constants as example A
NOTE: The specific reaction rate k1A is
(1)
defined with respect to species A.
NOTE: The specific reaction rate k2C is
(2)
defined with respect to species C.
The complex liquid phase reactions take place in a 2,500 dm3 CSTR. The feed is equal molar in A and B
with FA0 = 200 mol/min, the volumetric flow rate is 100 dm3/min and the reaction volume is 50 dm3.
Find the concentrations of A, B, C, and D exiting the reactor along with the exiting selectivity.
Plot FA, FB, FC, FD and SC/D as a function of V
Solution
Liquid CSTR
Mole Balances
Net Rates
Rate Laws
Relative Rates
Selectivity
Parameters
Would you like to see the results for Example B
Would you like to run for Example B
Example C: Gas Phase PFR, No Pressure Drop
Same reactions and rate laws as previous two examples
NOTE: The specific reaction rate k1A is
(1)
defined with respect to species A.
NOTE: The specific reaction rate k2C is
(2)
defined with respect to species C.
The complex gas phase reactions take place in a PFR. The feed is equal molar in A and B with FA0 = 10
mol/min and the volumetric flow rate is 100 dm3/min. The reactor volume is 1,000 dm3, there is no
pressure drop, the total entering concentration is CT0 = 0.2 mol/dm3 and the rate constants are
Plot FA, FB, FC, FD and C/D as a function of V
Solution
Gas Phase PFR, No Pressure Drop
Mole Balances
Net Rates
Rate Laws
Relative Rates
Selectivity
Stoichiometry
Parameters
Would you like to see the results for Example C
Would you like to run for Example C
Example D: Membrane Reactor with Pressure Drop
Same reactions and rate laws as previous two examples
NOTE: The specific reaction rate k1A is
(1)
defined with respect to species A.
NOTE: The specific reaction rate k2C is
(2)
defined with respect to species C.
The complex gas phase reactions take place in a catalytic packed bed with C diffusing out the sides. The
feed is equal molar in A and B with FA0 = 10 mol/min and the volumetric flow rate is 100 3/min. The reactor
volume is 50 dm3 and the total entering concentration is CT0 = 0.2 mol/dm3. There is pressure drop and
entering pressure is 100 atm and the rate constants are
The pressure drop parameter αρb = 0.0405 dm-3
The mass transfer coefficient for C is kcc = 2 min�1
Plot FA, FB, FC, FD and SC/D as a function of V for
(a) Case 1 CCsg = 0
(b) Case 2 CCsg ≠ 0,
Set Fosg = 0.1 mol/min and vary
(5 < < 10,000)
Are there a set of conditions whereby (CCsg < CC) and RC changes sign and Species C diffuses back into
the membrane reactor near the exit? Run the Polymath program when αρb = 0 and compare RC with the
base case when there IS pressure drop (αρb = 0.0405 dm-3)
Solution
Gas Phase Multiple Reactions in a Catalytic Packed Bed Membrane Reactor with Pressure Drop
Mole Balances
We also need to account for the molar rate desired product C leaving in the sweep gas FCsg
Rate Laws
a. Net rates, rate laws and relative rates same as Liquid and Gas Phase PFR
and Liquid Phase CSTR.
b. Transport Law
Case 1 Large sweep gas velocity
Case 2 Moderate to small sweep gas velocity
Vary to see changes in profiles
Case 2A Pressure Drop
Case 2B No Pressure Drop
Stoichiometry
We need to reconsider our pressure drop equation when one or more species diffuse out of the
reactor. Recall the pressure drop equation is
with
Warning!!
When mass diffuses out of a membrane reactor as there will be a decrease in the superficial
mass flow rate and hence G. To account for this decrease in calculating our pressure drop
parameter , we will take the ratio of the superficial mass velocity at any point in the reactor to
the superficial mass velocity at the entrance to the reactor. The superficial mass flow rates can
be obtained by multiplying the species molar flow rates, Fi, by their respective molecular
weights, MWi, and then summing over all species
Because the smallest molecule is the one diffusing out and has the lowest molecular weight,
we will neglect the changes in the mass flow rate down the reactor and will take as a first
approximation.
Isothermal (T = T0) and multiply both sides of the pressure drop equation by the bulk density,
ρb
Selectivity
Need to include C collected from sweep gas
Parameters
Would you like to see the results for Example D
Would you like to run for Example D
Example E: Liquid Semibatch
Same reactions, rate laws, and rate constants as example A
NOTE: The specific reaction rate k1A is
(1)
defined with respect to species A.
NOTE: The specific reaction rate k2C is
(2)
defined with respect to species C.
The complex liquid phase reactions take place in a semibatch reactor where A is fed to B with FA0 = 3
mol/min. The volumetric flow rate is 10 dm3/min and the initial reactor volume is 1,000 dm3.
The maximum volume is 2,000 dm3 and CA0 = 0.3 mol/dm3 and CB0 = 0.2 mol/dm3. Plot CA, CB, CC, CD
and SC/D as a function of time.
Solution
Liquid Phase Multiple Reactions in a Semibatch Reactor
Mole Balances
Net Rates, Rate Laws and relative rates � are the same as Liquid and Gas Phase PFR
and Liquid Phase CSTR.
Stoichiometry
Selectivity
Parameters
Would you like to see the results for Example E
Would you like to run for Example E
6.7 What's wrong with this solution?
6.1 ODE Solver Algorithm
Object Assessment of Chapter 6
* All chapter references are for the 4th Edition of the text Elements of Chemical Reaction Engineering .
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