Chapter 4

Isothermal Reactor Design

Part (2) Mole Balances in terms of

Concentration and Molar Flow Rates
2
 Mole Balances for Liquid Phase Reactions

3
 Mole Balances for Gas Phase Reactions

From Chapter 2:

dF j
= rj
dV

4
 From Chapter 3:
y

F j  T0  P
C j = CT 0  
FT  T  P0

From Chapter 4 (Part 1):

dy  T FT
=−
dW 2 y T0 FT 0

5
 Membrane Reactors

Membrane reactors can be used to achieve conversions greater

than the original equilibrium value. These higher conversions
are the result of Le Chatelier’s principle; you can remove the
reaction products and drive the reaction to the right.

To accomplish this, a membrane that is permeable to that

reaction product, but impermeable to all other species, is
placed around the reacting mixture.

6
 Membrane Reactors

Inert Membrane Reactor With Catalyst Pellets

On The Feed Side (IMRCF) Membrane Reactors

Catalytic Membrane Reactor (CMR) Schematic of IMRCF for mole balance

7
 Membrane Reactors
sweep
B W = ρbV = solids weight
FA0 ρb = (1-ϕ)ρC= bulk solids density
A,B,C ρC = density of solids

H2 H2
CBS

CB
A,C stay behind since they are too big
CBS: the concentration of B in the sweep gas channel
8
Mole Balance on Species A:
Species A: In – out + generation = 0

FA V − FA V +V + rAV = 0

dFA
= rA
dV
Mole Balance on Species B:

Species B: In – out by flow – out by diffusion + generation = 0

FB V − FB V +V − RB V + rB V = 0

dFB molar flow rate of B leaving through sides

= (rB − RB ) RB =
volume of reactor
dV
9
 ' molar flow rate through membrane  mol 
WB = kC (CB − CBS ) =  m2  s 
surface area of membrane

kC' : overall mass transfer coefficient (m/s)

membrane surface area DL 4  m2 

a= = 2 =  3
D
reactor volume
4
L D m 

kC = kC' a (s-1 )

RB = kCCB

Neglected most of the time Example 4-8

10
 Unsteady-State Operation of Stirred Reactors
 Batch reactors (done)
 Startup of a CSTR (to determine time acquired to reach steady-
state operation).
 Semibatch reactors

Concentration and conversion as a function of time ?

• Closed-form analytical solutions to the differential equations can be obtained only for
zero- and first-order reactions.
• ODE solvers must be used for other reaction orders
11
 Startup of a CSTR
 Always begin with the general mole balance equation:
dN A
FA0 − FA + rAV =
dt
 For liquid phase (  = 0) with constant overflow (V = V0) and  = V0 /0
dC A
C A0 − C A + rA = 
dt
 For 1st-order reaction (-rA = kCA)

dC A 1 + k C A0
+ CA =
dt  
 Which for the initial condition CA = 0 at t = 0 solves to

C A0   t 
CA = 1 − exp − (1 + k )  
1 + k    
12
 The steady-state concentration CAs:
C A0
C AS =
1 + k
 Letting ts be time necessary to achieve 99% of the steady-state concentration
CA = CAs :

ts = 4.6
1+ k

 For slow reactions with small k (k << 1):

ts = 4.6
 For rapid reactions with large k (k >> 1):

4 .6
ts =
k
13
 Semibatch Reactors
 Motivation: to enhance the selectivity in liquid-phase reactions
 Consider the following simultaneous reactions:

A + B ⎯⎯→
kD
D rD = k DC A2C B (Desired)
A + B ⎯⎯→
kU
U rU = kU C ACB2 (Undesired)

rD k D C A2C B k D C A
Instantaneous selectivity: S D / U = = 2
=
rU ku C AC B kU C B
Keep CA high and CB low.

→ Use semibatch reactor, which is charged with pure A and to which

B is fed slowly to A.
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  Semibatch reactors can be very effective in maximizing selectivity in
liquid phase reactions.

 The reactant that starts in the reactor is always the limiting reactant.


m

Liquid level and volume increase

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Overall mass balance:

 Rate   Rate   Rate of   Rate of 

 in  −  out  +  generation  = accumulation 
       
d ( V )
 00 - 0 + 0 =
dt

dV
For a constant density system,  0 =  and = 0
dt

Integrate with initial condition V = V0 at t = 0 yields:

16
V = V0 +  0t
 Writing The Semibatch Reactor Equations in Terms of Concentration

Mole Balance on Species A:

[in] – [out] + [gen] = [acc]

dN A
0 − 0 + rAV (t ) =
dt
dN A d [C AV ] dC A dV
= =V + CA
dt dt dt dt
dV
= 0
dt
dC A  0C A
= rA −
dt V
17
Mole Balance on Species B:

[in] – [out] + [gen] = [acc]

dN B
FB 0 − 0 + rBV =
dt

dN B d [CBV ] dCB dV
= =V + CB
dt dt dt dt
dV
FB0 = CB00 = 0
dt
dCB  0 ( CB 0 − CB ) At t = 0: the initial concentration of B, CBi = 0.
= rB +
dt V The concentration of B in the feed is CB0.

18 Example 4-9
Semibatch Reactors
Mass and Mole Balance Summary

 0C A
(1) dC A
= rA −
dt V
0 (C B 0 − C B )
(2) dCB
= rB −
dt V
 0 CC
(3) dCC
= rC −
dt V
 0C D
(4) dCD
= rD −
dt V
(5) V = V0 +  0t

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 Writing The Semibatch Reactor Equations in
Terms of Conversion
 Consider the following reaction in which B is fed to a vat containing only
A initially ⎯⎯→
A + B
⎯⎯ C + D

 The reaction is 1st order in A and 1st order in B

  CC CD 
− rA = k A C AC B − 
 K C 

 Number of Moles of A   Number of Moles of A   Number of Moles of A 

in the vat at time t  = in the vat initially  −  reacted up to time t 
     

NA = N A0 − N A0 X

20 X: moles of A reacted per mole of A initially in the vat

  Number of Moles of B  Number of Moles of B  Number of Moles of B  Number of Moles of B
in the vat at time t  = in the vat initially  + added to the vat  −  reacted up to time t 
       

t
NB = N Bi + F
0
B0 dt − N A0 X

For a constant molar feed rate and no B initially in the vat,

N B = FB0t − N A0 X

A mole balance on species A gives

dN A dX
rAV = = − N A0
dt dt

The number of moles of C and D:

N C = N Ci + N A0 X

N D = N Di + N A0 X
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 The concentrations of A, B, C, and D are

N A N A0 (1 − X ) NC N X
CA = = CC = = A0
V V0 + 0t V V0 + 0t

N B N Bi + FB 0t − N A0 X ND N X
CB = = CD = = A0
V V0 + 0t V V0 + 0t

Combining:

dX k (1 − X )( N Bi + FB 0t − N A0 X ) − ( N A0 X 2 / KC )
=
dt V0 + 0t

This equation needs to solved numerically to determine X(t)

22
Three Forms of the Mole Balances applied to Semibatch Reactors:
dN A
1. Molar Basis = rAV
dt
dN B
= FB 0 + rBV
dt

2. Concentration Basis dC A 
= rA − C A 0
dt V
0
= rB + (CB 0 − CB )
dCB
dt V

3. Conversion Basis dX − rAV

=
dt N A0

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 Equilibrium Conversion in a Semebatch Reactor
For reversible reactions the maximum attainable conversion (i.e., the equilibrium
conversion will change as the reaction proceeds because more reactant is continuously added
to the reactor. This addition shifts the equilibrium continually to the right toward more
product.

CCeCDe ( N Ce / V )( N De / V ) N Ce N De
KC = = =
C AeCBe ( N Ae / V )( N Be / V ) N Ae N Be

KC =
( N A0 X e )( N A0 X e )
N A0 (1 − X e )( FB 0t − N A0 X e )

N A0 X e2
K C=
(1 − X e )( FB 0t − N A0 X e )
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 Rearranging yields

N A0  X e2 
t=  KC X e + 
KC FB 0  (1 − X e ) 

2
 F t   F t  F t
KC  1 + B 0  −  KC  1 + B 0   − 4 ( KC − 1) KC B 0
 N A0    N A0   N A0
Xe =
2 ( KC − 1)

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