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 -rA = 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 dont
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 -rA = 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 20
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


1k t
CA
e

1
CA0
1 k

CA0
1 k

1 e
t 1k
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 t1k 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 1k
0.99
CA 0
1 k

Solve for ts to determine time to reach 99% of steady-state concentration
1 e s
t 1k
0.99 0.01 e s
t 1k
ln 0.01 ln e s
t 1k

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 1k
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
*Well 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+BC+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+BC+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 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
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.