Lecture 9

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.

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 Lecture 9
Balances in terms of molar flow rates
 Block 1: Mole Balances
Balance Equation on Every Species
 Block 2: Rate Laws
Relative Rates
Transport Laws
 Block 3: Stoichiometry
 Block 4: Combine

 Membrane Reactors:
Used for thermodynamically limited reactions
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 Review Lecture 1
Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction A→B)
Reactor Differential Algebraic Integral
NA NA
dN A
Batch dN A
= rAV t= 
dt rV
N A0 A
t
CSTR FA 0 − FA
V=
−rA FA
FA
PFR dFA V= 
dFA
= rA
dV FA 0
drA
 V
FA FA
dFA dFA
PBR
 dW
= rA W= 
FA 0
rA
3
W
4
 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.

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Membrane Reactors
Dehydrogenation Reaction:
C3H8 ↔ H2 + C3H6 A↔B+C

Thermodynamically Limited:
exothermic
Xe

Xe

XEB
T 6
 Membrane Reactors

Cross section of IMRCF Membrane Reactors

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Cross section of CRM Schematic of IMRCF for mole balance
 Membrane Reactors
sweep
B W = ρbV = solids weight
FA0 ρb = (1-ϕ)ρC= bulk solids density
A,B,C ρC = density of solids

B
𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑖𝑑𝑠 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑𝑠
𝜌𝑏 = ∗
𝑣𝑜𝑙𝑢𝑚𝑒 𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑖𝑑𝑠
H2 H2
CBS

CB
A,C stay behind since they are
too big
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 Membrane Reactors
Mole Balance on Species A:

Species A: In – out + generation = 0

FA V − FA V +V + rA V = 0

dFA
= rA
dV

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 Membrane Reactors
Mole Balance on Species B:

Species B: In – out – out membrane + generation = 0

FB V − FB V +V − RB V + rB V = 0

dFB
= ( rB − RB )
dV

moles of B through sides

RB =
volume of reactor
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 Membrane Reactors
' molar flow rate through membrane  mol 
WB = kC (CB − CBS ) =  m 2  s 
surface area of membrane

membrane surface area DL 4  m2 

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

RB = WB a = kC' aCB − CBS 

kC = kC' a
 mol 
RB = kC CB − CBS   m3  s 

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Neglected most of the time
 Membrane Reactors
Mole Balances:

(1) dFA
= rA
dV
(2) dFB
= rB − RB
dV
(3) dFC
= rC
dV
Rate Law:
 CBCC 
(4) rA = −k C A − 
 KC 
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 Membrane Reactors
− rA rB rC
Relative Rates: = =
1 1 1

Net Rates: (5) rA = −rB , rA = −rC

Transport Law: (6) RB = kC CB
Stoichiometry: (7 ) F
C A = CT 0 A (isothermal, isobaric)
FT
(8) CB = CT 0 FB
FT
(9) CC = CT 0 FC
FT
(10) FT = FA + FB + FC
13 Parameters: CTO = 0.2, FA0= 5, k = 4, KC = 0.0004, kC = 8
 Membrane Reactors
Example: The following reaction is to be carried out
isothermally in a membrane reactor with no
pressure drop. The membrane is permeable to
product C, but impermeable to all other species.
Inert Sweep Gas
H2 (C)
C6 H12  C6 H 6 + 3H 2 C H (A)
6 12
A B + 3C
C6H6 (B)
Inert Sweep Gas
For membrane reactors, we cannot use conversion. We
have to work in terms of the molar flow rates FA, FB, FC.
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 Membrane Reactors
Mole Balances C6 H12  C6 H 6 + 3H 2
A B + 3C
dFA
= rA
dW
Inert Sweep Gas
dFB  H2 (C)
= rB C6H12 (A)
dW
dFC C6H6 (B)
= rC  − kC CC Inert Sweep Gas
dW

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 Membrane Reactors

  C C 3

Rate Law: − rA = k A C A − B C

 K C 

Relative Rates: rA rB rC 

= =
−1 1 3

Net Rates: rB = −rA

rC  = −3rA
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 Membrane Reactors
Stoichiometry: P0
CT 0 =
Isothermal, no Pressure Drop RT0
FA
C A = CT 0
FT
FB
CB = CT 0
FT
FC
CC = CT 0
FT
FT = FA + FB + FC
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 Membrane Reactors
Combine: - Use Polymath

mol mol
Parameters: CT 0 = 0.2 3 FA 0 = 10
dm s
dm 3 dm 3
k A = 10 k C = 0 .5
kg cat s kg cat s
mol 2
KC = 200
dm6

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 Membrane Reactors
C6H12 (A)
C6H6 (B)
Ci
H2 (C)

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 End of Lecture 9

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 What is a membrane reactor?
 A membrane reactor is really just a plug-flow reactor that
contains an additional cylinder of some porous material
within it, kind of like the tube within the shell of a shell-and-
tube heat exchanger. This porous inner cylinder is the
membrane that gives the membrane reactor its name.
 The membrane is a barrier that only allows certain
components to pass through it. The selectivity of the
membrane is controlled by its pore diameter, which can be
on the order of Angstroms, for microporous layers, or on the
order of microns for macroporous layers.

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 Why use a membrane reactor?
 Membrane reactors combine reaction with separation to
increase conversion. One of the products of a given reaction
is removed from the reactor through the membrane, forcing
the equilibrium of the reaction "to the right" (according to
Le Chatelier's Principle), so that more of that product is
produced.
 Ex: Membrane reactors are commonly used in
dehydrogenation reactions (e.g., dehydrogenation of ethane),
where only one of the products (molecular hydrogen) is
small enough to pass through the membrane. This raises the
conversion for the reaction, making the process more
economical.

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 What kinds of membrane reactors are
available?
 Membrane reactors are most commonly used when a reaction involves
some form of catalyst, and there are two main types of these membrane
reactors: the inert membrance reactor and the catalytic membrane
reactor.
 The inert membrane reactor allows catalyst pellets to flow with the
reactants on the feed side (usually the inside of the membrane). It is
known as an IMRCF, which stands for Inert Membrane Reactor with
Catalyst on the Feed side. In this kind of membrane reactor, the
membrane does not participate in the reaction directly; it simply acts as
a barrier to the reactants and some products.
 A catalytic membrane reactor (CMR) has a membrane that has either
been coated with or is made of a material that contains catalyst, which
means that the membrane itself participates in the reaction. Some of the
reaction products (those that are small enough) pass through the
membrane and exit the reactor on the permeate side.

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