L5-1

Review: Derive –rA = f(XA)

rj nj ≡ stoichiometric coefficient
r A 
Relate all n•j  for products, ⊖ for reactants
rj to Cj

•
Batch: Flow:
Nj Nj0  n jNA0  XA  Fj Fj0  n jFA0  XA 
Relate all Cj   Cj  
Cj(XA) to V V u u
V(u)
Batch: Flow:
 P0   T  Z   Z  T   P0 
Relate all V  V0   T  Z  1   X A u  u01   X A    
V(u) to XA    0  0 
P  Z0  T0   P 

Batch
& C j0  n jCA0 XA  P   T0  Z0 
Put Cj     
together
Flow: 1   XA  0
P  T  Z 

Now that Cj is in terms of XA, we can write the rate law in terms of XA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-2

Review: Stoichiometric Tables

FA0 FA
FB0 In Out FB
b c d
FC0 A  B  C  D FC
FD0 a a a FD
FI0 FI
Feed rate Change in reactor Effluent rate from
Species
(mol/time) (mol/time) reactor (mol/time)
A FA0 -FA0XA FA = FA0 (1–XA)
B FB0 = QBFA0 nBFA0XA FB = FA0 (QB+ nBXA)
C FC0 = QCFA0 nCFA0XA FC = FA0 (QC+ nCXA)
D FD0 = QDFA0 nDFA0XA FD = FA0 (QD+ nDXA)
I FI0 = QIFA0 --- FI =FI0
Total FT0 dFA0XA FT = FT0 + dFA0XA
Fj0 C j0u0 C j0 y j0 nj ≡ stoichiometric coefficient d c b 
QJ     d =     1
FA0 CA0u0 CA0 y A0  for products, ⊖ for reactants a a a 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-3

L5: Reactor Design Recipe and

Reactor Scale-Up (Sizing)
Goal: Develop an algorithm that combines reactor design
equations with reaction rates for the design of different reactors

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-4

The Logic of Isothermal Reactor Design

1. Set up mole balance for In - Out + Generation = Accumulation
specific reactor V dNj
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
C j0  n jCA0 XA  P   T0  Z0 
rA  kC jn Cj     
3. Put Cj is in terms of 1   XA  0
P  T  Z 
XA and plug into rA n
 C j0  n jCA0 XA  P   T0  Z0  
(We will always look rA  k      
conditions where Z0=Z)  1   X A  P0   T  Z  
4. Plug rA into design eq and solve for the
time (batch) or volume (flow) required Today and next week!
for a specific XA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-5

Batch Reactor Operation (1)

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  kCA 2

 Stoichiometry (put CA in CA  CA0 (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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-6

Batch Reactor Operation (2)

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
 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
 kCA0 1  X A  Rearrange to get like variables together
2

dt
dX A  1  dX A k is constant for an
  kCA0dt    dt
1  XA  2
 A0  1  X A 
kC 2 isothermal reaction

Integrate  1  XA dX Time required to

t 1  XA 
  
A   dt   1 X   t achieve XA for
 A0  0 1  XA  A0  
kC 2 kC
0 A 2nd order rxn

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-7

Batch Reactor Operation (3)

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  kCA

 Stoichiometry (put CA in CA  CA0 (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
Mole balance as a function of conversion  N A0  kC A 0 1  X A  V0
dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-8

Batch Reactor Operation (4)

A→B -rA = kCA 1st order reaction rate
Calculate the time required for a conversion of XA in a constant V batch reactor
Mole balance as dX A
NA 0  kC A0 1  X A  V0 Evaluate to solve for time
in terms of XA: dt
dX A V0 dX A 1
  kC A0 1  X A    kC A0 1  X A 
dt NA0 dt C A0
dX A
  k 1  X A  Rearrange to get like variables together
dt

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

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

     dt    ln  t XA for 1st order rxn
 k  0 1  X A  0  k  1  XA
Remember: ln  1    ln 1  x 
 1 x 
Confused about the integration? See the next slide  
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-9

Batch Reactor Operation (4)

A→B -rA = kCA 1st order reaction rate
Calculate the time required for a conversion of XA in a constant V batch reactor

Integrate  1  XA dX A t
     dt
 k  0 1  X A  0

 1  1  1
    - ln 1  X A    t 0      ln 1  X A        ln 1  0    t  0
XA t

 
k 0 k k
0=ln(1)

 1  1  1 
     ln 1  X A    t    ln   t
k  k   1 X A 

 1
Remember: ln     ln  a 
a

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-10

Typical Cycle Time for a Batch

Polymerization
Total Cycle Time tt for a batch process is much longer than the reaction time
because it takes time to set up, heat, and clean the reactor each time it is used

Activity Time (h)

1. Charge feed to the reactor and agitate (tf) 1.5 - 3.0
2. Heat to reaction temperature (te) 0.2 – 2.0
3. Carry out reaction (tR) (varies)
4. Empty and clean reactor (tc) 0.5 – 1.0
Total time excluding reaction 3.0 – 6.0

Total Cycle Time tt = tf + te + tR + tc

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-11

CSTR Operation (1)

A→B -rA = kCA Liquid-phase 1st order reaction rate
Calculate the CSTR volume required to get a conversion of XA

FA0 X A
 Mole balance V
rA

 Rate law rA  kCA

 Stoichiometry (put CA in CA  CA0 (1  X A )

terms of X)
FA0 X Put FA0 in
V
 Combine kC A0 1  X A  terms of CA0

CA0u0 X A u0 X A Volume required

V V to achieve XA for
kCA0 1  X A  k 1  X A  st
1 order rxn
(u0u)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-12

Scaling CSTRs
• Chemical engineers are involved in scaling up a laboratory scale reaction
to the pilot plant scale or full-scale reactor
• If one knows the volume of the pilot-scale reactor required to achieve XA,
how is this information used to achieve XA in a larger reactor?
Suppose for a 1st order irreversible liquid-phase reaction:
u0 X A u0 X A
known: Vsmall  want: Vbigger 
k 1  X A  k 1  X A 
Want XA in the small reactor to be the same as XA in the bigger reactor
k in the small reactor is the same as k in the bigger reactor
u0 in the small reactor must be different from u0 in the bigger reactor
So the reactor volume V must be proportional to the volumetric flow rate u0
How? u0 X A Separate variables we will V XA
V 
k 1  X A  vary from those held constant u0 k 1  X A 

t 
XA Space time t (residence time) required to
t  V u0 
k 1  X A  achieve XA for 1st order irreversible rxn
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-13

Scaling CSTRs with Spacetime t

t 
XA Space time t (residence time) required to
k 1  X A  achieve XA for 1st order irreversible rxn

A→B -rA = kCA 1st order reaction rate

So if you know the spacetime t required to get a conversion of XA in a

CSTR, you can use that to achieve the same XA in a different size CSTR

What t is required to achieve a specific XA?

XA XA
Rearrange to get XA t   tk 
in terms of t: k 1  X A  1  XA 

 t k  t kXA  XA  t k  XA  t kXA  t k  X A 1  t k 

tk CSTR relationship between t and

  XA XA for 1st order liquid-phase rxn
1 t k
(isothermal and V = V0)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-14

Damköhler Number, Da
rA0 V rate of reaction at entrance reaction rate
Da   
FA0 entering flow rate of A convection rate

Estimates the degree of conversion that can be obtained in a flow reactor

First order irreversible reaction:
r V kCA0 V kV 1st order
Da  A0   Da   Da  kt irreversible
FA0 CA0u0 u0
reaction
t  V u0 Substitute
Second order irreversible reaction:
rA0 V kCA 0 V 2
kCA 0 V 2nd order
Da    Da   Da  kC A0t irreversible
FA 0 CA0u0 u0 reaction

How is XA related to Da in a first order irreversible reaction in a flow reactor?

From tk Da
previous X A   X A 
1 t k 1  Da
slide:
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-15

Damköhler Number, Da
rA0 V rate of reaction at entrance reaction rate
Da   
FA0 entering flow rate of A convection rate
Estimates the degree of conversion that can be obtained in a flow reactor

Da  kt
Relate XA to Da for a 1st tk  XA 
Da
order irreversible rxn in X  1storder
A
1 t k irreversible rxn 1  Da
a flow reactor:

If Da<0.1 for this 1st order irreversible rxn in a flow reactor, then
Da 0.1
XA   XA   0.091
1  Da 1  0.1

If Da>10 for this 1st order irreversible rxn in a flow reactor, then
Da 10
XA   XA   0.91
1  Da 1  10
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-16

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
FA0 X u0CA0 X
• Mole balance V 
rA rA

• Rate laws rA  kCA 2

• Stoichiometry CA  CA0 (1  X)
In terms of space time?
u0CA0 X V X
• Combine V
or u  t 
kCA 02 1  X  kC 1  X 
2 2
0 A0

X
1  2t kCA0   1  4t kCA0
In terms of conversion?
2t kCA0
2nd order liquid
irreversible reaction In terms of XA as a
X
1  2Da   1  4Da
function of Da? 2Da
Da  kC A0t
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-17

CA0u0
CSTRs in Series
CA1u u0  u Effluent of reactor 1 is input for
CA2u reactor 2, no change in u
A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and u and k are the same in both reactors (t1  t2  t & k1 = k2 = k)
Determine V1 for 1st CSTR using our standard procedure. For 2nd CSTR:
FA1  FA2
1. Mole balance CSTR2 V 
rA2
2. Rate law CSTR2 rA2  kCA2

3. Stoichiometry CSTR2 Skip this step for now.

u  C  CA2   C  CA2 
4. Combine for CSTR2 V  0 A1 or t = A1
kCA2 kCA2
Relate CA2 to t=
 CA1  CA2   t kC  CA1  CA2  t kCA2  CA2  CA1
A2
CA1, k, & t kCA2
C
 CA2 t k  1  CA1  CA2  A1
tk  1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-18

CA0u0
CSTRs in Series, CA1
CA1u u0  u Effluent of reactor 1 is input for
CA2u reactor 2, no change in u

A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and u and k are the same in both reactors (t1  t2  t & k1 = k2 = k)
What is CA1 in terms of t and k? We know for a single CSTR:

t k Put XA for 1
st
CA1 CA1
XA  CSTR in C A1  C A0 (1  X A1 )   1  X A1  X A1  1 
1  t k terms of C : CA0 CA0
A1
tk tk C A1 Solve  CA1 
Substitute:  X A1   1   t k   1   1  t k 
1 t k 1 t k C A0 for CA1:  CA0 

CA1  CA1  CA1  CA1  C A1

 t k  1 t k    t k     t k  1  1  t k   1
CA0  CA0  CA0  CA0  C A0
C A1 1 C A0
   C A1 
C A0 1  t k 1 t k
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-19

CSTRs in Series, CA2

CA0u0
CA1u Effluent of reactor 1 is
CA2u u0  u
input for reactor 2
A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and u and k are the same in both reactors (t1  t2  t & k1 = k2 = k)
CA1 CA0
Relate CA2 to k & t CA2  & CA1 
tk  1 1 t k

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

CA0 1st order irreversible

 CA2  rxn with V1 = V2, t1  t2
1  t k 2 and k1 = k2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-20

n CSTRs in Series
CA0u0
CA1u
CA2u u0  u

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
How is conversion related to the # of CSTRs in series?
Put CAn in terms of XAn CA0 1
CA0 1  X An    1  X An 
(XA at the last CSTR):
1  t k n 1  t k n
1 1 1st order irreversible liquid phase
 1  X An or 1   X An
1  t k n
1  Da  n rxn run in n CSTRs with identical
V, t and k
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L5-21

Isothermal CSTRs in Parallel

FA01
Mole Balance
 X  Subscript i
FA0 Vi  FA0i  Ai 
 rAi  denotes reactor i
FA02
same T, V, u
FA01 = FA02 = … FA0n
X 
V  FA0  A   X 1 =X 2 =... =X n =X
 rA 
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.