Multiple Reactions

! Objective
How to maximize desired product and to minimize undesired
product
How to design reactors when multiple reactions occur
! Outline
Four basic types of multiple reactions
Selectivity parameter
Parallel reactions
Series reactions
Develop the algorithm
Examples
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 Multiple Reactions
! Four Basic Type of Multiple Reactions
Parallel (competing)
Series (consecutive)
Complex
Independent

! Desired (D) and Undesired (U) Products

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 Selectivity and Reaction Yield
! Definition of Instantaneous Selectivity

! Definition of Overall Selectivity

! Definition of Instantaneous Yield

! Definition of Overall Yield

(batch) (flow)
For CSTR, instantaneous selectivity (yield) = overall selectivity (yield)
(example 6-1) 3
 Parallel Reactions

! Maximizing the Desired Product

If CA , SD/U Batch, PFR

If CA , SD/U CSTR

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! Effect of Temperature on Selectivity

Temp. as high as possible Temp. as low as possible

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 Example 6-1

E1 = 10,000 kcal/mole, E2 = 15,000 kcal/mole,

E3 = 20,000 kcal/mole, CA0 = 0.4M, v0 = 2.0 dm3/s

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Optimum CSTR followed by a PFR
If xA = 90% is required,

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 Reactor Selection and Operating Conditions

How to Maximize SD/U?

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 Example 6-2

CA and CB CA high; CB low

as high as possible

PFR or Batch
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CA and CB CA low; CB high
as low as possible

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 Series Reactions
At inlet
yethanol = 0.1%, yO2 = 1%,
Desired product yN2 = 98.9

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Homework P6-1

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 Algorithm for Solution of Complex
Reactions
! Combinations of parallel and series reactions
Numerical methods
Using Nj (Fj) rather than conversion
Liquid system: concentration
Gas system: molar flow rate

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 Net Rates of Reaction 1
A. Net Rate of Formation

B. Rate Laws

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 Net Rates of Reaction 2
C. Stoichiometry

eg.

D. Combination

Example 6-5 21
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 Stoichiometry: Concentration
! For Ideal Gas

For isothermal system with no pressure drop, i.e. T = T0, P = P0

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 Multiple Reactions in a Tubular Reactor
! Coupled ODEs for isothermal reactor without pressure drop

Numerical method is needed

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Example 6.6

Reaction species, n = 6, i.e. j = 1~6

Reaction number, q = 3, i.e. i = 1~3

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 Individual rate
of formation

Mole
balance

Net rate of
formation

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Net rate of
formation
Initial
conditions
Conc. vs. &
Flow rate Physical
parameters

! Most ODE solver will do all the substitutions !!

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 Summary for Multiple Reactions in a PFR

! For species j and reaction i in q reactions and n species

n equations

q equations

n*q equations

n equations

n equations

Example 6-7 n equations

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 Multiple Reactions in CSTR

! Mole balance
or (algebraic equations)
! Liquid phase: use Cj as variables
! Gas phase: use Fj as variables
! For N species participate in q reactions

Example 6-8 29
 Membrane Reactors to Improve Selectivity

! Membrane Reactors (MRs)

Shift the equilibrium toward completion
Increase selectivity
! Example 6-9: Compare Overall Selectivity in a MR and a PFR

B should be fed
through membrane

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Total molar flow rate of B:

Molar flow rate of B per unit volume:

Input table at P.350 31

! Molar flow rate along stream

! Selectivity profile

Homework P6-9 and 6-19 32

 Complex Reactions of Ammonia Oxidation
! Choice of variables
No volume change: Concentration
Volume change: Molar flow rate
! Example 6-10, Gas-phase reactions in PFR

Reaction species, n = 6, i.e. j = A~F

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Reaction number, q = 4, i.e. i = 1~4
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Let Program
combine these
equations

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 Sorting it All Out and The Fun Part
! How to determine the rate law from product distribution?
The best strategy to use to sort out all of the rate law parameters will
vary from system to system.
One general rule is to start an analysis by looking for species produced in
only one reaction; next, study the species involved in only two reactions,
then three, and so on.
! If intermediate products are free radicals
May not be possible to perform independent experiments to determine
rate law parameters
The analysis turns into an optimization problem statistic method
! The Fun Part
Learning how to maximize the desired product and minimize the
undesired product digital-age problems
Even more fun nonisothermal multiple reactions
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Problem 1 (Problem 6-12)

Species: n = 5, j = A ~ E
Rxn.: q = 3, i = 1 ~ 3

0.93

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! Individual rate laws for each species in each rxn. rij
r1 A r1B r1C
Rxn.1 : = = (c) r r1 A
= =
1
(0.7) = 0.233 mol/dm3 min
3 1 1 1C
3 3
r r r 2r2 D 1
Rxn. 2 : 2C = 2 A = 2 D r2C = = 3.0 0.512 0.10
2 1 3 3 3
r r r = 0.052 mol/dm3 min
Rxn. 3 : 3 D = 3C = 3 E
4 3 3 r3C = r3 E = k3 E C D CC = 2.0 0.049 0.51
(a) r1 A = k1 AC A = 7 0.10 = 0.7 mol/dm3 min = 0.050 mol/dm3 min
r2 D
r2 A =
1 1
= k 2 D CC2 C A = 3.0 0.512 0.10 (d)
3 3 3 r1D = 0
= 0.026 mol/dm3 min
r2 D = k 2 DCC2 C A = 3.0 0.512 0.10 = 0.078 mol/dm3 min
r3 A = 0
4 4
r3 D = r3 E = (0.050) = 0.067 mol/dm3 min
(b) r1 A 1 3 3
r1B = = (0.7) = 0.233 mol/dm3 min
3 3 (e) r1E = 0
r2 B = 0
r2 E = 0
r3 B = 0
r3 E = 0.050 mol/dm3 min
! Net rate laws for each species rj = rij
(f) rD = r1D + r2 D + r3 D = 0.011 mol/dm3 min
rA = r1 A + r2 A + r3 A = 0.726 mol/dm3 min
rB = r1B + r2 B + r3 B = 0.233 mol/dm3 min rE = r1E + r2 E + r3 E = 0.050 mol/dm3 min
rC = r1C + r2C + r3C = 0.131 mol/dm3 min 38
! Sizing for CSTR
(g)
FA0 FA + rAV = 0
FA0 FA v0 (C A0 C A ) 100(3 0.10)
V= = = = 400 dm 3
(rA ) (rA ) 0.726

Self Study: Try to finish Problem 6-12(h) ~ (j)

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 Problem 2 (Problem 6-14)

Species: n = 6, j = A ~ F
Rxn.: q = 3, i = 1 ~ 3

(v = v0) use concentration as variables

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(a) Mole Balance (design equation of PFR)
dC j rj
= (i = A ~ F ) Inputs for POLYMATH:
dV v0 Initial Values:
Mole ca = 1.5
Rate Laws: cb = 2.0
balance
rD1 = k D1C ACB2 cc = 0
rE 2 = k E 2C ACD cd = 0
ce = 0
rF 3 = k F 3CB CC2 cf = 0
Initial
rA = rD1 3rE 2
conditions
rB = 2rD1 rF 3
&
rC = rD1 + rE 2 2rF 3 Physical
rD = rD1 2rE 2 + rF 3 parameters
rE = rE 2
rF = rF 3 Net rate of
formation
Conversion of A:
C A0 C A
xA =
C A0

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Outputs from POLYMATH:

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(b) Mole balance (design equation of CSTR)
FA0 FA = rAV C A0 C A = rA Inputs for POLYMATH:
FB 0 FB = rBV or C C = r
B0 B B

Fi = riV (i = C ~ F ) Ci = ri (i = C ~ F ) Mole
balance
Rate Laws:
rA = rD1 3rE 2 rD1 = k D1C ACB2 Initial
rB = 2rD1 rF 3 conditions
rE 2 = k E 2C ACD
&
rC = rD1 + rE 2 2rF 3 rF 3 = k F 3CB CC2 Physical
rD = rD1 2rE 2 + rF 3
parameters
rE = rE 2
rF = rF 3

Combination:
f (C A ) = C A C A0 + (k D1C AC B2 + 3k E 2C AC D ) = 0
f (C B ) = C B C B 0 + (2k D1C AC B2 + k F 3C B CC2 ) = 0
f (CC ) = CC (k D1C AC B2 + k E 2C AC D 2k F 3C B CC2 ) = 0 Net rate of
f (C D ) = C D (k D1C AC B2 2k E 2C AC D + k F 3C B CC2 ) = 0 formation
f (C E ) = C E k E 2C AC D = 0
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f (C F ) = C F k F 3C B CC2 = 0
 Outputs from POLYMATH:

Answer: CA = 0.61, CB = 0.79, CC = 0.11, CD = 0.45, CE = 0.14, CF = 0.25 mol/dm3.

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(c) First case, where A is fed into B:

Mole Balance (design equation of Batch): Inputs for POLYMATH:

Initial Values:
dC A C CA ca = 1.5
= rA + v0 A0
dt V Mole cb = 2.0
dCi C balance cc = 0
= ri v0 i (i = B ~ F )
dt V cd = 0
where V = V0 + v0t ce = 0
Initial cf = 0
Rate Laws: same as (a), (b) conditions
&
Physical
parameters

Net rate of
formation

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Outputs from POLYMATH:

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(c) Second case, where B is fed into A:
Mole Balance (design equation of Batch): Inputs for POLYMATH:
Initial Values:
dC B C CB
= rB + v0 B 0 ca = 1.5
dt V Mole cb = 2.0
dCi C cc = 0
= ri v0 i (i = A, C ~ F ) balance
dt V cd = 0
where V = V0 + v0t ce = 0
Initial cf = 0
Rate Laws: same as (a), (b) conditions
&
Physical
parameters

Net rate of
formation

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Outputs from POLYMATH:

rD1 = k D1C ACB2

1. A fed into B rE 2 = k E 2C ACD
2. B fed into A rF 3 = k F 3CB CC2
In case 1, A is the main species in the reactor after a good amount of time. In case 2, B
is the main species after a time. The conversion of A is much greater in case 2 than in
case 1. In case 1, however, E and F are formed more early on.
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(d) Generalizations for varying B rD1 = k D1C ACB2
As B increases the outlet concentration rE 2 = k E 2C ACD
of species D and F increase, while the outlet rF 3 = k F 3CB CC2
concentration of species A, C and E
decrease. When B is large, reaction 1 and 3
are favored and when its small the rate of
reaction 2 will increase.

Self Study: Try to finish Problem 6-14(e) ~ (g)

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