L7-1

Review: 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 CA  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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-2

Review: 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 CA0  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.
 L7-3
Review: Isobaric, Isothermal, Ideal
Gas-Phase 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-4

Review: Effect of  on u 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
u0: volumetric flow rate
u varies if gas phase & moles product ≠ u  u 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 → u  u0 1   X A 
•  = 0 (mol product = mol reactants): u  u0: constant volumetric flow rate as XA
↑ < 0 (mol product < mol reactants): u < u0 volumetric flow rate ↓ as XA ↑
Q1: For an irreversible gas-phase reaction, how does the residence time and
XA change when  < 0?
a)They don’t
b)The residence time is longer & XA increases
c)The residence time is longer & XA decreases
d)The residence time is shorter, & XA decreases
e)The residence time is shorter & XA increases

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-5

Review: Effect of  on u 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
u0: volumetric flow rate
u varies if gas phase & moles product ≠ u  u 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 →
u  u0 1   X A 
•  = 0 (mol product = mol reactants): u  u0: constant volumetric flow rate as XA
increases
•  < 0 (mol product < mol reactants): u < u0 volumetric flow rate decreases as
XA increases
• Longer residence time than when u  u0
• Higher conversion per volume of reactor (weight of catalyst) than if u  u0
•  > 0 (mol product > mol reactants): u > u0 with increasing XA
• Shorter residence time than when u  u0
• Lower conversion per volume of reactor (weight of catalyst) than if u  u0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-6
Review: Isobaric, Isothermal, Ideal Rxn
GAS PHASE: in PFR
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
Be able to do these 5 steps, & solve for V

dX A rA
 Mole balance 
dV FA0
 Rate law rA  kCA 2
for ANY ORDER RXN

CA0 1  X A 
 Stoichiometry (put CA in CA 
terms of X) 1   XA

dX A k  C A0  1  X A 
2 2
 Combine 
dV 1   X A 2 FA0
V
FA0 XA
1   XA 2 dX

  A Integral A-7 in appendix
k CA0 0
2
1  XA  2
Gas-phase 2nd
FA0   1   2 X  order rxn in
V 2 1    ln 1  X A    2 X A   A 
k CA02     1  XA



PFR no DP,
DT, or DZ
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-7

Review: 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 FA0  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 FA 0 1   X A  2
 P0 

 Relate P/P0 to W dP   T   P0 
     1   X A 
(Ergun equation) dW 2  T0   P P0  
dy 
Ergun Equation can be simplified   1   X A 
by using y=P/P0 and T=T0: dW 2y
Simultaneously solve dXA/dW and dP/dW (or dy/dW) using Polymath
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-8

Review: Ergun Equation

dP   T   P0  Calculates pressure drop in a packed bed.
     1   X 
dW 2  T0   P P0   A This equation can be simplified to:

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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-9

L7: Unsteady-State Isothermal

Reactor Operation: CSTR Start-Up
and Semi-Batch Reactors
Semi-batch CBu0

A A+B

V0 V0 + u0t Vf

start time t end

• Time required to reach steady-state after CSTR start-up

• Predicting concentration and conversion as a function of time
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-10

Start-Up of a Fixed-Volume CSTR

Isothermal (unusual, but simple case), well-mixed CSTR
Unsteady state: concentrations vary with time & accumulation is non-zero
Goal: Determine the time necessary to reach steady-state operation

CA0u0 u0CA
In - Out + Generation = Accumulation
moles A in CSTR
dNA changes with
FA0  F A  rA V 
dt time until steady
state is reached

Use concentration rather than conversion in the balance eqs

dNA  C A0u0  C Au0  rA V  dNA  1 

CA0u0  C A u0  rA V   
dt V dt V
Divide by V to convert dNA to dCA

V C A0 CA dC A Multiply dCA
    rA  CA0  CA  rA  
u0   dt by  dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-11

CSTR Start-Up: 1st Order Reaction

dC A dC A
C A0  CA  rA   Combine C  C  k C   
dt rA  kCA A0 A A
dt
Integrate this eq to find CA (t) while 1st order rxn in CSTR is at unsteady-state:
Bring variables to dC A 1
one side & factor   C A0  CA 1  k  
dt 
dCA  1   CA0 
    1  k    CA  Put like variables
dt    1  k   with their integrals

  CA0 
CA t 1  k    CA  
 C
dCA
 dt   1  k    1  k 
  ln 0 t
0 A0  C 0  C  
1  k  A A0  0
 1  k  
 

1k  t
CA
e 

 1
CA0
1  k 

 CA0 
 1  k  

1  e 
 t 1k  
 CA

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-12

CSTR Start-Up: 1st Order Reaction

dCA We integrated this eq to find CA (t) while
CA0  CA  kC A  
dt CSTR of 1st order rxn is in unsteady-state:

0

At steady state,  CA0  1  e t1k    C  C A0  C
t is large and:  1  k  A
1 k  AS

Is this consistent with steady C  C  kC    dCA No accumulation

A0 A A
state balance eq for CSTR? dt at steady state
Yes, same! 0
CA0
 CA0  CA  kCA  0   CAS Goal: combine start-up and SS eqs
1  k  to estimate time to reach SS (ts)
In the unsteady state,  CA0 
when CA = 0.99CAS:

 1  k  

1  e 
 t s 1k  
 0.99 
 CA 0 
 1  k 
 
Solve for ts to determine time to reach 99% of steady-state concentration
 1 e s
 t 1k  
 0.99  0.01  e s 
 t 1k  
 ln 0.01  ln e s 
  t 1k  
  
 1  k   time to reach 99% of steady-state
 4.6   t s   4.6  ts
   1  k concentration in terms of k
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-13

CSTR Start-Up: 1st Order Reaction

 1  k  
 C



1  e  
 C A0  t 1k 
A

In the unsteady state, the time to 

t  4.6
reach CA = 0.99CAS is: 1  k

When k is very small When k is very big 4.6

t  4.6 ts 
(slow rxn), 1>>k: s (fast rxn), 1<<k k

63% of the steady-state 

CA = 0.63CAS
concentration is achieved at: 1  k

99% of the steady-state 

4.6 CA  0.99CAS
concentration is achieved at: 1  k

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-14
Better Selectivity in a Semi-Batch
Reactor
To enhance selectivity of desired product over side product
2
P rP  kpCA CB
kP
A  B  Desired product P
2
 S rS  kSCA CB
kS
A  B  Undesired side product S

Instantaneous selectivity, SP/S, is the ratio of the relative

rates*:
rP kPCA 2CB kP CA
SP/S   
rS k S CA CB 2 k S CB

Higher concentrations of A favor formation of the desired product P

Higher concentrations of B favor formation of the undesired side product S
To maximize the formation of the desired product:
Slowly feed B into the reactor containing A
Commonly used in bioreactors, when the enzyme is inhibited by excess substrate
*We’ll look at this concept of instantaneous selectivity in more detail in L9
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-15

Semi-Batch Reactor Design Equation

CBu0 Do a mole balance on A since it does not enter or leave
the reactor (assume the reactor is well-mixed)
In - Out + Generation = Accumulation
dNA
FA0  FA  rA V 
dt
dNA
0  0  rA V 
dt
V0 + u0t
Use whatever units are most convenient (NA, CA, XA, etc)
Convert NA to CA using:
dC A V
NA
 CA  NA  CA V  rA V 
V dt

dC A dV 2 parts: how CA changes with

 rA V  V  CA
dt dt t and how V changes with t

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-16

Semi-Batch Reactor Design Equation

CBu0 Do a mole balance on A since it does not enter or leave
the reactor (assume the reactor is well-mixed)
In - Out + Generation = Accumulation
dNA
0  0  rA V  t  
dt
dC A dV 2 parts: how CA changes with t
 rA V  V  CA
dt dt and how V changes with t
V0 + u0t
Reactor volume at any time can be found with a mole balance
In - Out + Generation = Accumulation
d   V  u = u0 dV
0u0  0  0   u0   V0  u0t  V
dt   0 dt
dC A
Substitute:  rA V  V  C Au0 Rearrange to get in terms of dCA/dt
dt
dCA CAu0 dCA
 rA V  CAu0  V  rA   Balance on A
dt V dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-17

Semi-Batch Reactor Design Equation

CBu0 Mole Balance on B
In - Out + Generation = Accumulation
dNB
FB0  0  rB V 
dt
dNB dNB
  rB V  FB0   rB V  FB0
dt dt
dVCB d
V0 + u0t    CB V   rB V  FB0
dt dt

dV dCB dV
 CB V  rB V  CB0u0 u0  Substitute
dt dt dt
dCB
 CBu0  V  rB V  CB0u0 Rearrange to get in terms of dCB/dt
dt

dCB u0  CB0  CB 
  rB  Balance on B
dt V
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-18

Semi-Batch Reactor Design Equation:

C uB 0
in Terms of NA
In - Out + Generation = Accumulation
dNA
0  0  rA V 
dt
dNA
 rA V Substitute V  V0  u0t
dt
dNA Reactor design eq. provided
 rA  V0  u0 t 
V0 + u0t dt that rA is a function of NA
 NA  NB NA NB
-rA = kACACB  rA  k  V  V  rA   k
   V  u t 2 0 0
dNA dNA NA NB
  rA V   k
dt dt V0  u0 t
dNB dNB NANB
NB comes from BMB:  rA V  FB0   k  FB0
dt dt V0  u0 t
The design eq in terms of XA can be messy. Sometimes it gives a single
equation when using Nj or Cj gives multiple reactor design equations.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-19
Improving Yields of Reversible Rxns with
Semi-Batch Reactors
Semi-batch FD

A+B
A+B⇌C+D

V0 V0 - u0t Vf

To improve product yield in a reversible reaction: A  l   B l  C l   D  g

• Start with A(l) and B(l) in the reactor
• D(g) bubbles out of the liquid phase, pushing the equilibrium to the right
and forcing the reaction to go to completion Boil off water to
Common industrial reaction: produce high
MW polymer
+ n + H2O
nylon
n
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-20
Improving Yields of Reversible Rxns with
Semi-Batch Reactors
Semi-batch FD

A+B
A+B⇌C+D

V0 V0 - u0t Vf

To improve product yield in a reversible reaction: A  l   B l  C l   D  g

• Start with A(l) and B(l) in the reactor
• D(g) bubbles out of the liquid phase, pushing the equilibrium to the right
and forcing the reaction to go to completion

How do we account for the loss of product D in the material balance?

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L7-21

Loss of Mass in Semi-Batch Reactor

D(g) A l  B l C  l   D  g elementary rxn u = u0    0
Overall Mass balance:
In - Out + Generation = Accumulation
m  
dm g 
u0  m  0   gas leaving reactor
dt  time 
m m
 V ↑want in terms of dV/dt
V 
V0 + u0t u0 m dm  1  m dV
Divide mass balance by       u0  
  dt     dt
Relate ṁ to a rate: From stoichiometry, rD = -rA
moles Next, convert mass moles
rA  Conversion 1: rA  V  
volume  time units to: time time
Conversion 2: mass
molesD 
massD
 molesD MWD   massD rA  V  MW  m
MWD time
Substitute for ṁ
dV r V MWD 
 u0  A One of the diff. eq. that are simultaneously solved
dt  (by Polymath)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.