Review: 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   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   jCA0 XA  P   T0  Z0  
(We will always look rA  k     
conditions where Z0=Z)  1   X A  0
P  T  Z 
4. Plug rA into design eq and solve for the
Examples of combining rates &
time (batch) or volume (flow) required
design eqs follow!
for a specific XA
 Review: 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
 rA V
Be able to do these 4 steps, and

 Mole balance NA0

then integrate to solve for time

dt

 Rate law rA  kCA 2

for ANY REACTION

 Stoichiometry (put CA in C A  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

Integrate this equation in
order to solve for time, t
NA0
dX A
dt
 
 k CA02 1  X A  V0
2

1  XA 
   t
kCA0  1  X A 
 Review: CSTR Operation
A→B -rA = kCA 1st order reaction rate
Calculate the CSTR volume required to get a conversion of XA
FA 0 X A
 Mole balance V
 rA

 Rate law rA  kCA

 Stoichiometry (put CA in CA  CA0 (1  XA )

terms of X)
FA0 X Put FA0 in
V
 Combine kCA0 1  X A  terms of CA0

CA00 XA 0 XA Volume required

V V to achieve XA for
kCA0 1  X A  k 1  X A  st
1 order rxn
Be able to do these steps for any order reaction!
 Review: Scaling CSTRs
• 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 rxn:
0 XA 0 XA
known: Vsmall  want: Vbigger 
k 1  XA  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
0 in the small reactor must be different from 0 in the bigger reactor
So the reactor volume must be proportional to the volumetric flow rate 0
0 X A Separate variables we will V XA
V 
k 1  X A  vary from those held constant 0 k 1  X A 
Eq is for a 1st order rxn only!
XA Space time t (residence time) required to
t  V 0  t
k 1  X A  achieve XA for 1st order irreversible rxn
Be able to do this for any order rxn!
 Review: 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 CA00 0
reaction
t  V 0 Substitute
Second order irreversible reaction:
rA0 V kCA 0 V2
kCA0 V 2nd order
Da    Da   Da  kCA0t irreversible
FA 0 CA00 0 reaction

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

From tk Da If Da < 0.1, then XA < 0.1
XA   XA 
slide L6-7: 1 t k 1  Da If Da > 10, then XA > 0.9
Review: Sizing CSTRs for 2nd Order Rxn
A→B -rA = kCA2 Liquid-phase 2nd order reaction rate
Calculate the CSTR volume required to get a conversion of XA
FA0 X 0CA0 X
• Mole balance V 
rA rA

• Rate laws rA  kCA 2

Be able to do these steps!
• Stoichiometry CA  CA0 (1  X)
In terms of space time?
0CA0 X V X
• Combine V
or   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
Eq is for a2nd order
liquid irreversible rxn In terms of XA as a
X
1  2Da   1  4Da
Da  kC A0t function of Da? 2Da
 Review: n CSTRs in Series
CA00
CA1
CA2 0  

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 XA CA0 1
CA0 1  XA    1  XA 
(XA at the last CSTR):
1  t k n 1  t k n
1 1 1st order irreversible liquid phase
 1  XA or 1   XA
1  t k 
n
1  Da n rxn run in n CSTRs with identical
V, t and k
Review: Isothermal CSTRs in Parallel
FA01
Mole Balance
 X  Subscript i
FA0 Vi  FA0i  Ai 
 rAi  denotes reactor i
FA02
same T, V, 
FA01 = FA02 = … FA0n
X 
V  FA0  A   X1 = X 2 = ... = Xn = 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 
F total molar flow rate
FA0i  A0 
n # of CSTRs  XA 
Molar flow rate of each CSTR V  F A0  

 A
r
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
 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  kCA 2

ORDER RXN

 Stoichiometry (put CA in C A  CA0 (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 CA0 2
 0 1  XA  2
0  2  1 X
k CA0  A  
See Appendix A for integrals
frequently used in reactor design
Liquid-phase 2nd order reaction in PFR
 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  kCA 2

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

terms of X)
dX A

 
k C A02 1  X A 
2

 Combine
dW FA0

FA0 XA dX A W  XA 
FA0
   dW  2  1 X 
W

k C A0 2


0 1  X A 2 0 
k C A0  A 
Liquid-phase 2nd order reaction in PBR
 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
• No stirring element, so flow must be turbulent

FA0 FA

C j0   jCA0 XA  P   T0  Z0  C j0   jCA0 XA
GAS PHASE: C j       Cj 
1   XA  P0   T  Z  1   XA
1 1 1
Stoichiometry for basis species A:
CA0  CA0 XA CA0 1  XA 
CA   CA 
1   XA 1   XA
 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   XA  dX
2

  A Integral A-7 in appendix
k CA0 0
2
1  XA  2

FA0   1   2 X   Gas-phase 2nd

V 2 1    ln 1  X A    2 X A   A 


2 
k CA0   

1  X A  order rxn in PFR
  no DP, DT, or DZ
 Effect of  on  and XA
NTf  NT0 Change in total # moles at X A  1
 
NT0 total moles fed
: expansion factor, the fraction of change in V per mol A reacted
0: volumetric flow rate
 varies if gas phase & moles product ≠    1   X  Z  T   P0 
0 A    
moles reactant, or if a DP, DT, or DZ occurs  0  T0   P 
Z
No DP, DT, or DZ occurs, but moles product ≠ moles reactant →
  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
• Longer residence time than when   0
• Higher conversion per volume of reactor (weight of catalyst) than if   0
•  > 0 (mol product > mol reactants):  > 0 with increasing XA
• Shorter residence time than when   0
• Lower conversion per volume of reactor (weight of catalyst) than if   0
 Pressure Drop in PFRs & PBRs
C j0   jCA0 XA  P   T0  Considering ideal gas
GAS PHASE: Cj    
1   XA  P0   T 
phase behavior (Z0=Z)

Concentration is a function of P so pressure drop is important in gas phase rxns

Why? Take a 1st order reaction A → B in a PBR with –r’A = kCA
Substitute concentration C  CA0 X A  P   T0 
r 'A  k A0   
of A into the rate law: 1   XA  P0   T 
If P drops during the reaction, P/P0 is less than one, so CA ↓ & the rxn rate ↓
Use the differential forms of the design equations to address pressure drop
For tubular PFR PBR
reactors: dXA moles dXA moles
 rA  
 
FA0 F r '
dV dm3  min 
A0
dW A
 g catalyst min
Pressure drops are especially common in reactions run in PBRs
→ we will focus on PBR applications
 Pressure Drop in PBRs
GAS PHASE: A → B -r’A = kCA2 2nd order reaction rate
Calculate dXA/dW for an isothermal ideal gas phase reaction with DP
dX A
 Mole balance F A0  r 'A
dW
 Rate law r 'A  kCA 2
CA0 1  X A   P 
 Stoichiometry (put CA in CA   
terms of X) 1   X A  P0 

 Combine dX A


k C A02  1  XA 2  P 2
 
dW FA0 1   X A  2
 P0 
This eq. is solved simultaneously
A0  A
2 2
with an eq. that describes how the  dX A  kC 1  X  P 
pressure drops as the reactant dW 0 1   XA 2  P0 
moves down the reactor
Function of XA and pressure We need to relate P/P0 to W
Ergun Equation relates P to W
dP   T   P0 
     1   XA  This equation can be simplified to:
dW 2  T0   P P0  

dy  T
Differential form of Ergun equation   1   XA   
for pressure drop in PBR: dW 2y  T0 
P NTf  NT0 2 0
y    y A0 
P0 NT0 A c c 1    P0
volume of solid
1    : fraction of solid in bed =
total bed volume

AC: cross-sectional area C: particle density

: constant for each reactor, calculated using a complex
equation that depends on properties of bed (gas density,
particle size, gas viscosity, void volume in bed, etc)
: constant dependant on the packing in the bed
Gas Phase Reaction in PBR with ΔP
GAS PHASE: A → B -r’A = kCA2 2nd order reaction rate
Calculate dXA/dW for an isothermal ideal gas phase reaction with DP
dX A
 Mole balance F A0  r 'A
dW

dX A kC A0 1  X A   P 
2 2
 Combine with rate law 
and stoichiometry dW 0 1   X 2  P0 
A

Relate P/P0 to W dP   T   P0 
     1   XA 
dW 2  T0   P P0  

Ergun Equation can be simplified by using y=P/P0 and T=T0:

dy 
  1   X A 
dW 2y
Simultaneously solve dXA/dW and dP/dW (or dy/dW) using Polymath
 Analytical Solutions to P/P0
Sometimes P/P0 can be calculated analytically. When T is constant and  = 0:

dy  T dy 
    1   X A    Evaluate
dW 2y  T0  0 dW 2y
1 1

To pressure change
P
y
P0 W
2 P P0
 2ydy   dW   2ydy    dW  y   W
P
1
1 0
P0
From no pressure change
2
P 
P
 1  W Only for isothermal
    1   W
P0 rxn where =0
 P0 
 Pressure Drop Example
GAS PHASE: A → B -r’A = kCA2 2nd order reaction rate
This gas phase reaction is carried out isothermally in a PBR. Relate the
catalyst weight to XA dX A N  NT0 1  1
FA0  r 'A   Tf  0
dW NT0 1
CA0  CA0 X A  P   T0  P
CA      CA  CA0 1  X A   
1   XA  P0   T   P0 
0 1
P Plug
 = 0 and isothermal, so:  1  W CA  CA0  CA0 X A 1   W
P0 into CA

 
Plug into PBR dX A dX A 2
design eq: FA0 2
 kCA  FA 0  k CA0 1  X A  1   W
dW dW
Simplify, integrate, and solve for XA in terms of W or W in terms of XA:
FA0 XA dX A W
  1   W  dW
dX A
 kCA0 1  X A  1   W  
2 2
 FA0 
dW kCA02 0 1  XA  2
0
 Pressure Drop Example
A→B -r’A = kCA2 2nd order gas phase rxn non-elementary rate
This gas phase reaction is carried out isothermally in a PBR. Relate the
catalyst weight to XA
FA0 XA dX A W  A0  X A   W 
   1   W  dW   1 
2    
W
kC 0 1  X 
2
0 k C A0  1  X A   2 
A0 A
 XA    W   kCA0 
Solve for XA   1 X   W 1   
 A   2  
 0 
  W   kC A0    W   kC A0 
 XA  W 1     W 1    XA
 2   0   2   0 
  W   kC A0    W   kC A0 
 XA  W 1    A
X  W 1   
 2   0   2   0 
  W   kCA0 
1   
 2   0   20  X A 
 XA  1 1 
  W   kCA0  Rearrange  1  X 
1  1    eq. for W: W   A0  
kC A
 2   0  