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Chapter 6

Design for Single Reactions

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6.1 Size Comparison of Single Reactors
• Batch Reactor
- Advantages : low cost and flexibility of operation
- Disadvantages : high labor and handling cost time consuming
poor quality control
- appropriate to produce small amounts of material and to produce
many different products from one equipment

• MFR VS PFR for first and second-order rxns


- nth-order rate law
1 dN A
− rA = − = kC An
V dt

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- For MFR
 C A0V  C A0 X A 1 X A (1 + ε A X A ) n
τ m =   = = n −1
 FA0 m − rA kC A0 (1 − X A ) n

- For PFR
 C A0V  X A (1 + ε X )
n
X A dX 1
τ p =   = C A0 ∫ A
= n −1 ∫0
A A
dX A
 FA0 p 0 − rA kC A0 (1 − X A )

  1 + ε X n 
 C An 0V   X A  A A
 
 
(τ C A0 ) m  FA0  m
n −1
  1 − X A   m
= =
(τ C A0 ) p  C A0V 
n −1 n
 X A  1 + ε X n 
 
F  ∫0


 A0  p   1 − X A 
A A
 dX A 
 p

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- with constant density ( ε = 0 ), the performance ratio:

 XA 
 (1 − X ) n 
(τ C An −01 ) m  m , n ≠ 1
= A

(τ C An −01 ) p  (1 − X A )1−n − 1
 − 
 n 1 p
 XA 
 
(τ C A0 ) m
n −1
 1 − X A m
or = , n =1
(τ C A0 ) p − ln(1 − X A ) p
n −1

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< Fig 6.1 >

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1. Vm > Vp, Vm/Vp ↑ as n ↑

2. At small XA, reactor performance is only slightly affected by flow type.

The performance ratio increases very rapidly at high XA

3. Density variation during reaction affects design.

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Variation of Reactant Ratio for Second-order Reactions

A+ B → P
M = C B 0 / C A0

− rA =− rB =kC ACB


= rA kC A=
CB kC A2 , when =
M 1


= rA kC A=
CB ( kCB 0 )=
C A k ' C A , when M > 1 (CB ≅ CB 0 )

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General Graphical Comparison

- for all nth order rxn (n > 0)


Vm > Vp

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6.2 Multiple-Reactor Systems
• PFR in Series and/or in Parallel
 N PFRs in Series

Vi X i dX
=∫
F0 X i −1 − r

V N
Vi V1 + V2 +  + VN X N dX
=∑ = =∫
F0 i =1 F0 F0 0 −r

- N PFRs in series with a total volume V gives same conversion


as a single PFR of volume V

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 N PFRs in parallel
- V of a single PFR = Total V of individual units if the feed is
distributed with same composition
- V/F or τ must be same for each parallel line.

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• Equal Sized MFRs in series

- As the number of MFRs in series increases, the system approaches


plug flow

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- Consider a series of N equal-sized MFRs
(Density change is negligible; ε A = 0 and t = τ )

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• First-order rxns

C0Vi Vi C0 ( X i − X i −1 )
τi = = =
F0 υ0 − rAi
Ci −1 − Ci Ci −1 C0
τi = , = 1 + kτ i , = (1 + kτ i ) N ε = 0
kCi Ci CN

N  C0 
1/ N

τ N reactors = Nτ i =   − 1
k  C N  

for N → ∞, τ N reactors = τ p

1 C0
τ p = ln
k C XA dX A C A dC
τ p = C A0 ∫ = −∫ A
0 − rA C A 0 kC
A

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MFR

PFR

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• Second-Order Rxns
1
CN = (−2 + 2 − 1 +  + 2 − 1 + 2 1 + 4C0 kτ i
4kτ i

~ derive it

- for PFR
C0
= 1+ C0 kτ P
C

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• MFRs of different sizes in series

 Finding the conversion in a given system

V C0 − C1
τ 1 = t1 = = ε = 0
υ (−r )1
1 ( − r )1 1 ( − r )i
− = − =
τ 1 C1 − C0 τ i Ci − Ci −1

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 Determining the best system for a given conversion

- Minimum size of two mixed flow reactors in series

C0 − C1 C0 − C0 (1 − X 1 ) C0 X 1
τ1 = = =
(−r )1 (−r )1 (−r )1

τ1 X1
=
C0 ( − r )1

τ2 X 2 − X1
=
C0 ( − r )2

- Total reactor volume is as small as possible rectangle KLMN is


as large as possible
- Choose Xi to maximize the area of the rectangle KLMN

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• Maximization of Rectangles

- The area of rectangle between x-y axes at point M(x,y)


A = xy
- max area
dA = 0 = ydx + xdy
dy y
− =
dx x
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- the area is maximized when M is at the point where the slope of curve
= slope of diagonal NL
- Optimum size ratio of two reactors

- Optimum size ratio of two MFR in series


for 1st order rxn: equal size best
for n > 1: smaller come first
for n < 1: larger come first

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• Reactors of Different Types in Series
MFR – PFR – MFR

V1 X 1 − X 0 V2 X 2 dx V3 X 3 − X 2
= , =∫ , =
F0 (−r )1 F0 X 1 − r F0 (−r )3

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- Best arrangement of a set of ideal reactors
1. When rate-concentration curve rises monotonically (n>0),
- If the rate-concentration curve is concave (n>1), reactant
concentration should be as high as possible
- If the rate-concentration curve is convex (n<1), reactant
concentration should be as low as possible

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6.3 Recycle Reactor: PFR
• Recycle Ratio (R)

Volume of fluid returned to the reactor entrance


R=
Volume leaving the system
R = 0 (~PFR)
R = ∞ (~MFR)

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V X A 2 = X AF dX
=∫ A
FA′0 X A1 − rA

FA′0 = freed rate of A if the stream entering the reactor


(fresh feed + recycle) is not unconverted
- at point L

FA′0 = RFA0 + FA0 = ( R + 1) FA0


1 − C A1 / C A0
X A1 =
1 + ε AC A1 / C A0

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FA1FA0 + FA3 FA0 + RFA0 (1 − X Af )
At point K, C A1 = = =
υ1 υ0 + Rυ f υ0 + Rυ0 (1 + ε A X Af )
 1 + R − RX Af 
= C A0  
 1 + R + Rε X 
 A Af 
 R 
X A1 =   X Af
 R +1

• The performance eqn for recycle reactors

V X Af dX A
= ( R + 1) ∫ R  for any ε A
FA0   X Af − r
 R +1  A

- if density changes are negligible

C A0V C Af dC A
τ= = −( R + 1) ∫C A 0 + RC Af for ε A = 0
FA0 R +1 − rA

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• Extreme cases,

V X Af dX A
= ( R + 1) ∫ R
FA0 X Af − r
R +1 A

R=0 R=∞

V X Af dX V X
=∫ A = Af
FA0 A − rA FA0 − rAf

PFR MFR

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- for first-order rxn, ε A = 0

kτ  C A0 + RC Af 
= ln  
R +1  ( R + 1)C Af 

- for second-order rxn, − rA = kC A2 , ε A = 0

kC A0τ C A0 (C A0 − C Af )
=
R + 1 C Af (C A0 + RC Af )

<Fig 6.16>
<Fig 6.17>

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6.4 Autocatalytic Reactions

A + R → R + R, − rA = kC AaCRr

C A0

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• PFR VS MFR, No Recycle.

1. At low XA, MFR > PFR


2. At high XA, PFR >MFR

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• Optimum Recycle Operations:
Optimum recycle ratio: an optimum particular recycle ratio
that minimizes the reactor volume or space time

d (τ / C A0 ) τ X Af R + 1
= 0 for =∫ dX A
dR C A0 X Ai ( − r )
A

X Af dX A
1 ∫ X Ai −rA
=
−rA X Ai
( X Af − X Ai )

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KL << PQ KL = PQ KL >> PQ

1 1
- value of feed (KL) = value in the reactor as a whole (PQ)
− rA − rA

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• Reactor Combinations

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Chapter 7
Design for Parallel Reaction

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Qualitative Discussion
about Product Distribution
k1 R (desired product)
A
k2 C (unwanted product)
dC R
rR = = k1C Aa1
dt
dCS
rS = = k 2C Aa2
dt

- relative rates of formation : as large as possible


rR dC R k1 a1 − a2
= = CA
rS dCS k 2

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If a1>a2, desired reaction order > unwanted reaction order
high CA → R/S ↑
Batch or PFR favored; minimum reactor size

If a1<a2, desired reaction order < unwanted reaction order


low CA to favor formation of R
Large MFR required

If a1=a2, two reactions are of same order

rR dC R k 2
= = = constant
rS dCS k1

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- product distribution is fixed by k2/k1 unaffected by the reactor type!

- Control of product variation by varying k2/k1


1. T change  activation energies
2. Catalyst  depressing or acceleration specific reaction

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Qualitative Treatment of Product
Distribution and of Reactor size
• Instantaneous fractional yield of R

 moles R formed  dCR


ϕ = =
 moles A reacted  − dC A
• Overall fractional yield of R
(= mean of the instantaneous fractional yields)
- represents the product distribution at the reactor outlet

 all R formed  CRf CRf


Φ= = = = ϕ in reactor
 all A reacted  C A0 − C Af ( − ∆C A )

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• For PFR
−1 C Af 1 C Af
ΦP =
C A0 − C Af ∫C A0 A ∆C A
ϕdC = ∫ C A0
ϕdC A

• For MFR

Φ m = ϕ evaluated at C Af

• Overall fractional yields

 dΦ p  1 C Af
Φ m =  
 dC A at CAf
, Φp =
∆C A ∫
C A0
Φ m dC A

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• For N MFRs in series

ϕ1 (C A0 − C A1 ) +  + ϕ N (C A, N −1 − C A, N ) = Φ N ,mixed (C A0 − C AN )
ϕ1 (C A0 − C A1 ) +  + ϕ N (C A, N −1 − C A, N )
Φ N ,mixed =
C A0 − C AN
CRf = Φ (C A0 − C Af )

Area = CRf

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• The selectivity
 moles of desired product formed 
selectivity =  
 moles of unsired material formed 

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Chapter 8
Potpourri of Multiple Reactions

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8.1 Irreversible First-order
Reactions in Series
A 
k1
→ R 
k2
→S
rA = −k1C A
rR = k1C A − k2CR
rS = k2CR
• Qualitative Discussion About Product Distribution
1) Uniformly irradiated
2) Continuously withdrawn, irradiated and returned

<Fig 8.1> <Fig 8.2>


Maximum R formation Minimum R formation

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- For irreversible reactions in series, max possible amount of
intermediates is obtained.
if fluids of different compositions and at different stages
of conversion are not allowed to mix.

- PFR or Batch should give a max R yield because there is


no mixing of fluid streams of different compositions.

- MFR should not give as high a yield of R as possible


because a fresh stream of pure R is being mixed with
an already reacted fluid in the reactor.

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Quantitative Treatment,
PFR or Batch Reactor
A 
k1
→ R 
k2
→S
• For PFR CA
= e − k1τ
C A0
CR k1
= ( e − k1τ − e − k2τ )
C A0 k2 − k1

C S = C A0 − C A − C R

- max intermediate : k2 /( k2 − k1 )
CR ,max  k1 
= 
C A0  k2 
1 ln( k2 / k1 )
τ p ,opt =
=
klog mean k2 − k1
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Quantitative Treatment, MFR
• MB at steady state
input = output + disappearance
- for A
FA0 = FA + ( − rA )V , υC A0 = υC A + k1C AV
V CA 1
= τ m = t, =
υ C A0 1 + k1τ m

- for R υCR 0 = υCR + ( − rR )V

0 = υCR + ( −k1C A + k2CR )V

CR k1τ m
=
C A0 (1 + k1τ m )(1 + k2τ m )

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- for S
C A + C R + CS = C A0 = constant
CS k1k 2τ m
=
C A0 (1 + k1τ m )(1 + k 2τ m )

- max R
dC R 1
= 0, τ m ,opt =
dτ m k1k 2

Then,
C R ,max 1
=
C A0 [(k 2 / k1 )1/ 2 + 1]2

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Remarks:
- Except when k1 = k2, always τ p < τ m
- when k2/k1 ↑, τ p / τ m ↑
- CR,max in PFR > CR,max in MFR

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 CR 
- Φ   : PFR > MFR
 CA 
- if k2/k1 <<1, high XA and probably dispense with recycle of
unused reactant

 CR 
- if k2/k1 >>1, Φ   ↓ at low XA
 CA 
- To avoid unwanted S instead of R, small XA,
separation of R and recycle of unused reactant needed

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8.2 First-order followed
by Zero-order Reaction
A
=

k1

n1 1 =
R 
k2
n2 0
→S

− rA =
k1C A k 2 / C A0
K=
=
rR k1C A − k2 k1

- for Batch or PFR with CR0 = CS0 = 0

CA CR k2
e − k1t ,
= = − k1t
1− e − t
C A0 C A0 C A0
CR ,max 1 1
=
1 − K (1 − ln K ), tR ,max = ln
C A0 k1 K

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8.2 First-order followed
by Zero-order Reaction

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8.3 Zero-order followed
by First-order reaction

A
=

k1

n1 0=
R 
k2
n2 1
→S

− rA =
k1
rR= k1 − k2CR A present k2
K=
rR = −k2CR A absent k1 / C A0

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- for Batch or PFR with CR0 = CS0 = 0

CA k1t
= 1− ,
C A0 C A0
CR 1 C
= (1 − e − k2t ) t < A0
C A0 K k1
1 C
= (e K − k 2 t − e − k 2 t ) t < A 0
K k1
C R ,max 1 − e − K C
= , t R ,max = A0
C A0 K k1

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8.5 Reversible Reactions
• Reversible first-order reactions


→ R ←
A ←
 
→S

T
B

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8.6 Irreversible Series-Parallel Reactions
• Two-step Irreversible Series-Parallel Reactions

A + B →
k1
R

R + B →
k2
S

S + B →
k3
T
etc

or A +→ R +
B ,k1
→ S +
B ,k 2
→ T
B ,k 3

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Two-step Irreversible Series-Parallel Reactions
A + B →
k1
R

R + B →
k2
S
- irreversible, bimolecular, constant density
dC A
rA = = −k1C ACB
dt
dCB
rB = =
−k1C ACB − k2CRCB
dt
dCR
=
rR = k1C ACB − k2CRCB
dt
dCS
=
rS = k2CRCB
dt

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• Qualitative Discussion about Product Distribution
(a) Add A slowly to B

(b) Add B slowly to A

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(c) Mix A and B rapidly
- when A is kept uniform in composition
- when the concentration level of B has no effect on the path
of reaction and on the distribution of products

+A R
+B
A  +B
→ R  →S B
+R S

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Quantitative Treatment, PFR or Batch Reactor
• The intermediate (R) is the desired product

rR dC R k 2C R
= = −1+
rA dC A k1C A

CR 1   CA 
k 2 / k1
C A  k2
=   − , ≠1
C A0 1 − k2 / k1  C A0  C A0  k1
 
CR C A C A0 k 2
= ln , =1
C A0 C A0 C A k1

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


k2 /( k2 − k1 )
CR ,max  k1  k2
=   , ≠1
C A0  k2  k1
CR ,max 1 k2
= = 0.368, = 1
C A0 e k1
MB on A :
C A0 + C R 0 + C S 0 = C A + C R + C S
or ∆C A + ∆CR + ∆CS = 0
MB on B :
∆CB + ∆CR + 2∆CS = 0

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


• Quantitative Treatment, MFR

C A 0 − C A −C R
=τm =
− rA − rR

C A0 − C A −C R
=τm =
k1C A − CB k2CRCB − k1C ACB

C A (C A 0 − C A )
CR =
C A + ( k2 / k1 )(C A0 − C A )

C R ,max 1
=
C A0 [1 + ( k2 / k1 )1/2 ]2

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)
POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)
8.7 The Denbigh Reactions
and their special cases
1 3 − rA =
k12C A
A R S
2 4 =
rR k1C A − k34CR
T U k12= k1 + k2
rS = k3CR
rT = k2C A k34= k3 + k4
rU = k4CR

C A0 + CR 0 + CS 0 + CT 0 + CU 0 = C A + CR + CS + CT + CU
S
A+R S A R A R S
U
R R
T
A
A S
T

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


Batch or Plug Flow Reactors
CA
= exp( −k12t )
C A0

CR k1 C
= [exp( −k12t ) − exp( −k34t )] + R 0 exp( −k34t )
C A0 k34 − k12 C A0

CS k1k3  exp( −k34t ) exp( −k12t )  k1k3


=  −  +
C A0 k34 − k12  k34 k12  k12k34
C k C
+ R 0 3 [1 − exp( −k34t )] + S 0
C A0 k34 C A0

CT k C
= 2 [1 − exp( −k12t )] + T 0
C A0 k12 C A0
CU
=
C A0

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


If C=
R0 C=
S0 C=
T0 C=
U0 0

CA k1   CA 
k34 / k12
CA 
=   − 
C A0 k12 − k34  C A0  C A0 
 
k34 /( k34 − k12 )
CR ,max k1  k12 
=  
C A0 k12  k34 
ln(k34 / k12 )
tmax =
k34 − k12

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


Mixed Flow Reactors
CA 1
=
C A0 1 + k12τ m
CR k1τ m C 1
+ R0
C A0 (1 + k12τ m )(1 + k34τ m ) C A0 (1 + k34τ m )

CS k1k3τ m2 C k3τ m C
= + R0 + S0
C A0 (1 + k12τ m )(1 + k34τ m ) C A0 (1 + k3τ m ) C A0

CT k2τ m Cτ 0
+ +
C A0 (1 + k12τ m ) C A0
CU
=
C A0

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)


At the optimum

CR ,max  k1  1
=   ⋅
C A0  2
k [( k 34 / k12 )1/ 2
+ 1]2

1
τ m ,R ,max =
( k12 / k34 )1/2

POSCO 전문교수연구실, Environmental Remediation Engineering Lab. (www.knuerel.org)