KIL 2009 & KKEK 2220

CHEMICAL REACTION
ENGINEERING I

DR MUHAMAD FAZLY ABDUL PATAH

ROOM W-02-01
[email protected]
Lecture 8

• Block 1: Mole Balances

• Block 2: Rate Laws
• Block 3: Stoichiometry
• Block 4: Combine

• Isothermal Reactor Design

2
 Isothermal Reactor Design

Goal:
To develop an algorithm that combines reactor design
equations with reaction rates for the design of different
reactors
The Logic of Isothermal Reactor Design
1. Set up mole balance for In - Out + Generation = Accumulation
specific reactor V dN j
Fj0  F j   rjdV 
dt

Batch CSTR PFR

2. Derive design eq. in FA0 X A X A dX
XA
terms of XA for each dX A V= A
t =NA0  -rA V =FA0 
reactor 0 -rA V 0 -rA

3. Put Cj is in terms of C j0   jCA0 X A  P   T0  Z0 

rA  kC jn Cj     
XA and plug into rA 1   XA  0
P  T  Z 
n
 C j0   jC A0 X A  P   T0   Z0  
rA  k     
 1   X A  P0   T   Z 

4. Plug rA into design eq and solve for the

Today and next week!
time (batch) or volume (flow) required
for a specific XA
 Isothermal Batch Reactor Operation
A→B -rA = kCA2 2nd order reaction rate
Calculate the time required for a conversion of XA in a constant V batch reactor

dX A
 Mole balance NA0  rA V
dt

 Rate law rA  kC A 2

 Stoichiometry (put CA in C A  C A0 (1  X A )
terms of X)

 Combine NA0
dX A
dt
 
 k C A 02 1  X A  V
2

Batch Volume is constant, V=V0

 NA0
dX A
dt
 
 k C A02 1  X A  V0
2
 Isothermal Batch Reactor Operation
dX A
 kC A 02 1  X A  V0
2
Evaluate NA 0
dt
dX A 2 V0 dX A 2 1
  kC A02 1  X A    kC A02 1  X A 
dt NA0 dt CA 0

dX A
 kC A0 1  X A 
2
 Rearrange to get like variables together
dt

 1  dX A k is constant for an
   dt
 kCA0  1  X A 
2 isothermal reaction

Integrate  1  XA dX t 1  XA  Time required to

  
A   dt   1 X   t achieve XA for
 A0  0 1  X A  A0  
kC 2 kC
0 A 2nd order rxn
 Isothermal Batch Reactor Operation
A→B -rA = kCA 1st order reaction rate
Calculate the time required for a conversion of XA in a constant V batch reactor
dX A
 Mole balance NA0  rA V
dt

 Rate law rA  kC A

 Stoichiometry (put CA in C A  C A0 (1  X A )
terms of X)

dX A
 Combine NA0  kC A 0 1  X A  V
dt

Batch Volume is constant, V=V0

dX A
 NA0  kC A 0 1  X A  V0
dt
 Isothermal Batch Reactor Operation
Mole balance as in terms of XA:
dX A
NA 0  kC A0 1  X A  V0 Evaluate to solve for time
dt

dX A V dX A 1
  kC A0 1  X A  0   kC A0 1  X A 
dt NA0 dt C A0

dX A
  k 1  X A  Rearrange to get like variables together
dt
 1  dX A
   dt k is constant for an isothermal reaction
 k  1  X A 

Integrate  1  XA dX A t
 1 1 Time required to
     dt    ln t achieve XA for 1st
 k  0 1  X A  0  k  1  XA
order rxn
 1 
Note that: ln     ln 1  x 
 1 x 
 Homework:
Study Textbook Example 4-1
Isothermal CSTR
A→B -rA = kCA Liquid-phase 1st order reaction rate
Calculate the CSTR volume required to get a conversion of XA

F X
 Mole balance V  A0 A
rA

 Rate law rA  kC A

 Stoichiometry (put CA in C A  C A0 (1  X A )
terms of X)
FA0 X
V
 Combine kC A0 1  X A 

CA00 X A 0 X A Volume required to

V V achieve XA for 1st
kCA0 1  X A  k 1  X A  order rxn (0)
Design of Isothermal CSTR
Rearrange and define a new term, t
V XA

0 k 1  X A 

XA
t  V 0  t 
k 1  X A 

Space time t (or residence time) required to achieve XA for 1st

order irreversible rxn
Design of Isothermal CSTR

Rearrange to get XA in terms of t:

tk
  XA
1 t k

Substitute XA in CA  CA0 (1  X A ) to write CA in terms of t:

𝐶𝐴0
𝐶𝐴 =
1 + t𝑘

CSTR relationship between t, XA and CA0 for 1st order liquid-phase

rxn (isothermal and V = V0)
 Damköhler Number, Da
Is a dimensionless number that estimates the degree of conversion
that can be obtained in a flow reactor
rA0 V rate of reaction at entrance reaction rate
Da   
FA0 entering flow rate of A convection rate

First order irreversible reaction:

r V kC A0 V kV 1st order
Da  A0   Da  irreversible
FA0 CA00 0 reaction
Substitute t  V 0  Da  kt

Second order irreversible reaction:

2 2nd order
rA0 V kC A 0 V kC A 0 V
Da    Da   Da  kC A0t irreversible
FA 0 CA00 0 reaction
Damköhler Number, Da
Now we can write XA and CA in terms of Da:
Da  kt
tk  XA 
Da
XA  1st order
1 t k irreversible rxn 1  Da

If Da<0.1, conversion X is low:

Da 0.1
XA   XA   0.091
1  Da 1  0.1

If Da>10, conversion X is high:

Da 10
XA   XA   0.91
1  Da 1  10
 Sizing CSTRs for 2nd Order Rxns
A→B -rA = kCA2 Liquid-phase 2nd order reaction rate
Calculate the CSTR volume required to get a conversion of XA
F X  C X
• Mole balance V  A0  0 A0
rA rA

• Rate laws rA  kC A 2

• Stoichiometry C A  C A0 (1  X)
0CA0 X V X
• Combine V t 
kCA 02 1  X 
2 or 0 kC A0 1  X 
2

In terms of conversion? X
1  2t kCA0   1  4t kCA0
2t kCA0
In terms of XA as a function of Da? 2nd order liquid

X
1  2Da   1  4Da irreversible reaction

2Da Da  kC A0t
 Isothermal CSTRs in Series
CA00
CA1 0  
CA2

A first order reaction is carried out isothermally using 2 CSTRs that are
the same size, and  and k are the same in both reactors (t1  t2  t &
k1 = k2 = k)
Effluent of reactor 1 is input for reactor 2, no change in 

Determine V1 for 1st CSTR using our standard procedure. For 2nd CSTR:
FA1  FA2
Mole balance CSTR2 V
rA2

0  CA1  CA2   CA1  CA2 

V or t =
kCA2 kCA2

C
 CA2 t k  1  CA1  CA2  A1
tk  1
Isothermal CSTRs in Series
What is CA1 in terms of t and k?

tk
XA  Put XA for 1st CSTR in terms of CA1:
1 t k

We know for a single CSTR:

C A1 C
C A1  C A0 (1  X A1 )   1  X A1  X A1  1  A1
C A0 C A0

tk tk C
Substitute:  X A1   1  A1
1 t k 1 t k C A0

Solve for CA1:

C A1 1 C A0
   C A1 
C A0 1  t k 1 t k
Isothermal CSTRs in Series
Since:
C A1 C
C A2  & C A1  A0
tk  1 1 t k

Substitute CA1 into CA2 equation:

C  1 
CA 2   A 0   
 1  t k   t k  1 

CA0 1st order irreversible rxn with

 CA2 
1  t k 2 V1 = V2, t1  t2 and k1 = k2
n Isothermal CSTRs in Series
CA00
CA1
CA2 0  

Therefore for 1st order irreversible liquid-phase rxn run in n-CSTRs

with identical V, t and k
CA0
For n identical CSTRs, then: CAn 
1  t k n

Rate of disappearance of A in the nth reactor:

CA0
rAn  kCAn  k
1  t k n
n Isothermal CSTRs in Series
How is conversion related to the number of CSTRs in series?

Write CAn in terms of XAn (XA at the last CSTR):

C A0 1
C A0 1  X An    1  X An 
1  t k n 1  t k n

1 1
 1  X An or 1   X An
1  t k 
n
1  Da  n

Note that this equation is derived for 1st order n-CSTRs

21
Second order reaction in CSTRs
Conversion of second order reaction of CA is given by:
23
 Isothermal CSTRs in Parallel
FA01
Mole Balance
X  Subscript i
FA0 Vi  FA0i  Ai 
 rAi  denotes reactor i
FA02
If the T, V,  are constant
for all CTSRs:
X  FA01 = FA02 = … FA0n
V  FA0  A 
 rA   X 1 = X 2 =... = X n = X
V total volume of all CSTRs  rA1  rA2  ...  rAn  rA
Vi  
n # of CSTRs
V FA0  X Ai 

Volume of each CSTR n n  rAi 
FA0 total molar flow rate
FA0i  
n # of CSTRs X 
Molar flow rate of each CSTR V  FA0  A 
 rA 
Conversion achieved by any one of the reactors in parallel is the same
as if all the reactant were fed into one big reactor of volume V
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 L6-34

Liquid Phase Reaction in PFR

LIQUID PHASE: Ci ≠ f(P) → no pressure drop
2A → B -rA = kCA2 2nd order reaction rate
Calculate volume required to get a conversion of XA in a PFR
dX A rA
integrate & solve for V for ANY


Be able to do these 4 steps,

 Mole balance
dV FA0

 Rate law rA  kC A 2

ORDER RXN

 Stoichiometry (put CA in C A  C A0 (1  X A )
terms of X)
dX A

 
k C A02 1  X A 
2

 Combine
dV FA0

FA0 XA
dX A V  XA 
FA0
    dV  V

k C A0 2
 0 1  X A  2
0  2  1 X 
k CA0  A 
Liquid-phase 2nd order reaction in PFR
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L6-35

Liquid Phase Reaction in PBR

LIQUID PHASE: Ci ≠ f(P) → no pressure drop
2A → B -r’A = kCA2 2nd order reaction rate
Calculate catalyst weight required to get a conversion of XA in a PBR
Be able to do these 4 steps, integrate

dX A r 'A
& solve for V for ANY ORDER RXN

 Mole balance 
dW FA0

 Rate law r 'A  kC A 2

 Stoichiometry (put CA in C A  C A0 (1  X A )
terms of X)
dX A

 
k C A02 1  X A 
2

 Combine
dW FA0

FA0 XA dX A W FA0  XA 
   dW  2  1 X 
W

k C A02 

0 1  X A 
2
0 
k C A0  
A 

Liquid-phase 2nd order reaction in PBR

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L6-36

Isobaric, Isothermal, Ideal Rxns in

Tubular Reactors
Gas-phase reactions are usually carried out in tubular reactors (PFRs & PBRs)
• Plug flow: no radial variations in concentration, temperature, & -rA

FA0 FA

Stoichiometry for basis species A:

CA0  CA0 X A CA0 1  X A 
CA   CA 
1   XA 1   XA

- assuming constant temperature and pressure

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L6-37

Isobaric, Isothermal, Ideal Rxn in PFR

GAS PHASE: Ci = f() → no DP, DT, or DZ
2A → B -rA = kCA2 2nd order reaction rate
Calculate PFR volume required to get a conversion of XA
dX A rA
 Mole balance 
dV FA0
 Rate law rA  kC A 2
C A0 1  X A 
 Stoichiometry (put CA in CA 
terms of X) 1  X A

dX A k  C A0  1  X A 
2 2
 Combine 
dV 1   X 2 F A A0

V
FA0 XA
1   X A  dX
2

  A Integral A-7 in appendix
k C A0 0
2
1  X A  2

FA0   1   2 X   Gas-phase 2nd

V 2 1    ln 1  X A    2 X A   A   order rxn in PFR

k C A02    1  XA


  no DP, DT, or DZ
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L6-38

Isobaric, Isothermal, Ideal Rxn in PFR

dX A k  C A0  1  X A 
2 2

dV 1   X 2 F A A0

Integrate and re-arrange in terms of V:

V
FA0 XA
1   X A 2 dX


k C A0 2
 0 1  X A  2 A

FA0   1   2 X 
V 2 1    ln 1  X A    X A  
2 A 

k C A02    1  XA




(Integral A-1 in appendix)

Gas-phase 2nd order rxn in PFR with no DP, DT

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L6-39

Effect of  on  and XA
Recall that:
 Z  T   P0 
  0 1   X A      
 0  T0   P 
Z

When there is no DP, DT but moles product ≠ moles reactant (i.e.  ≠ 0):

  0 1   XA 

Rearrange to obtain the ratio between v and v0

𝑣
= 1 + 𝜀 𝑋𝐴
𝑣0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L6-40

Effect of  on  and XA
When:   0 1   XA 

•  = 0 (mol product = mol reactants);

  0: constant volumetric flow rate as XA increases

•  < 0 (mol product < mol reactants):  < 0 volumetric flow rate
decreases as XA increases thus:
• Longer residence time than when   0
• Higher conversion per volume of reactor (weight of catalyst)
than if   0

•  > 0 (mol product > mol reactants):  > 0 volumetric flow rate
increases with increasing XA thus:
• Shorter residence time than when   0
• Lower conversion per volume of reactor (weight of catalyst)
than if   0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
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 Homework:
Study Textbook Example 4-3
Tutorial Questions:

Will be informed later

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