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 – Thursday 2/7/2013
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
𝑑𝑁𝐴 𝑑𝑁𝐴
Batch
=𝑟 𝐴 𝑉 𝑡= ∫
𝑑𝑡 𝑁 𝐴0
𝑟𝐴𝑉
t
CSTR V

𝐹𝐴 FA
𝑑𝐹𝐴 𝑑𝐹𝐴
PFR
𝑑𝑉
=𝑟 𝐴 𝑉=∫
𝐹 𝐴0
𝑑𝑟 𝐴
V
𝑑 𝐹 𝐴 FA
𝐹𝐴
𝑑𝐹𝐴
PBR
𝑑𝑊
=𝑟 ′ 𝐴 𝑊=∫ ′
3 𝐹 𝐴0 𝑟𝐴
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 = ∗
𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑜𝑡𝑎𝑙 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

𝐹 𝐴|𝑉 − 𝐹 𝐴|𝑉 + Δ 𝑉 +𝑟 𝐴 Δ𝑉 =0

𝑑𝐹𝐴
=𝑟 𝐴
𝑑𝑉

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 Membrane Reactors
Mole Balance on Species B:

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

𝐹 𝐵|𝑉 − 𝐹 𝐵|𝑉 + Δ 𝑉 − 𝑅 𝐵 Δ 𝑉 +𝑟 𝐵 Δ𝑉 =0

𝑑𝐹𝐵
=(𝑟 𝐵 − 𝑅 𝐵 )
𝑑𝑉

moles of B through sides

𝑅𝐵=
volume of reactor
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 Membrane Reactors
′
𝑊 𝐵 =𝑘 (𝐶 𝐵 − 𝐶 𝐵𝑆 )=
𝐶
surface area of membrane [ ]
molar flow rate through membrane 𝑚𝑜𝑙
2
𝑚 ⋅𝑠

[ ]
2
membrane surface area 𝜋 𝐷𝐿 4 𝑚
𝑎= = =
reactor volume 𝜋𝐷
2
𝐷 𝑚3
𝐿
4
𝑅 𝐵 =𝑊 𝐵 𝑎=𝑘 𝑎 [ 𝐶 𝐵 −𝐶 𝐵𝑆 ]
′
𝐶
′
𝑘𝐶=𝑘 𝑎𝐶

𝑅 𝐵 =𝑘𝐶 [ 𝐶 𝐵 −𝐶 𝐵𝑆 ]
[ 𝑚𝑜𝑙
𝑚3 ⋅ 𝑠 ]
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Neglected most of the time
 Membrane Reactors
Mole Balances:
𝑑𝐹𝐴
( 1) =𝑟 𝐴
𝑑𝑉
𝑑 𝐹𝐵
( 2) =𝑟 𝐵 − 𝑅 𝐵
𝑑𝑉
𝑑 𝐹𝐶
(3 ) =𝑟 𝐶
𝑑𝑉
Rate Law:

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[
( 4 ) 𝑟 𝐴 =− 𝑘 𝐶 𝐴 −
𝐶𝐵 𝐶𝐶
𝐾𝐶 ]
 Membrane Reactors
−𝑟 𝐴 𝑟 𝐵 𝑟 𝐶
Relative Rates: = =
1 1 1

Net Rates: ( 5 ) 𝑟 𝐴 =−𝑟 𝐵 , 𝑟 𝐴=− 𝑟 𝐶

Transport Law: ( 6 ) 𝑅 𝐵 =𝑘𝐶 𝐶 𝐵
❑
𝐹𝐴
Stoichiometry: ( 7 ) 𝐶 𝐴=𝐶 𝑇 0
❑
(isothermal, isobaric)
𝐹𝑇
𝐹𝐵
( 8 ) 𝐶 𝐵 =𝐶 𝑇 0
𝐹𝑇
𝐹𝐶
( 9 ) 𝐶 𝐶 =𝐶 𝑇 0
𝐹𝑇
( 10 ) 𝐹 𝑇 =𝐹 𝐴 + 𝐹 𝐵 + 𝐹 𝐶
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Parameters: CTO = 0.2, FA0= 5, k = 4, KC = 0.0004, kC
 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 F A, FB, FC.
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 Membrane Reactors
Mole Balances C6 H12  C6 H 6  3H 2
A B  3C
𝑑𝐹𝐴 ′
=𝑟 𝐴
𝑑𝑊
Inert Sweep Gas
𝑑𝐹𝐵 ′  H2 (C)
=𝑟 𝐵 C6H12 (A)
𝑑𝑊
𝑑 𝐹𝐶 C6H6 (B)
=𝑟 𝐶 ′ − 𝑘𝐶 𝐶 𝐶 Inert Sweep Gas
𝑑𝑊

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 Membrane Reactors

[ ]
3
Rate Law: ′ 𝐶𝐵 𝐶 𝐶
−𝑟 𝐴 =𝑘 𝐴 𝐶 𝐴 −
𝐾𝐶
′ ′ ′
Relative Rates: 𝑟𝐴 𝑟𝐵 𝑟 𝐶
= =
−1 1 3

Net Rates:
′ ′
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𝑟 =−𝑟 𝐴
𝐵
 Membrane Reactors
Stoichiometry: 𝑃0
𝐶 𝑇 0=
Isothermal, no Pressure Drop 𝑅𝑇0
𝐹𝐴
𝐶 𝐴 =𝐶 𝑇 0
𝐹𝑇
𝐹𝐵
𝐶 𝐵=𝐶 𝑇 0
𝐹𝑇
𝐹𝐶
𝐶 𝐶 =𝐶 𝑇 0
𝐹𝑇
𝐹 𝑇 =𝐹 𝐴 +𝐹 𝐵 + 𝐹 𝐶
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 Membrane Reactors
Combine: - Use Polymath

𝑚𝑜𝑙 𝑚𝑜𝑙
Parameters: 𝐶 𝑇 0=0.2 𝐹 𝐴 0=10
𝑑𝑚
3
𝑠
3 3
𝑑𝑚 𝑑𝑚
𝑘 𝐴 =10 𝑘𝐶 =0.5
𝑘𝑔 𝑐𝑎𝑡 𝑠 𝑘𝑔 𝑐𝑎𝑡 𝑠
2
𝑚𝑜 𝑙
𝐾 𝐶 =200 6
𝑑𝑚

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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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