Spring 2024

Chemical Reaction Engineering

CHE 348

Week 10
 Week 9 / Lecture 1

CH. 5. ISOTHERMAL REACTOR DESIGN: CONVERSION

• Pressure Drop in Reactors (Repeated)

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 • Second order reaction (2𝐴→𝐵)
• Liquid phase
PBR • Isothermal
• Δp=0
Calculate catalyst weight (W) required to get XA

Step Equation Remark

Mole balance 𝑑𝑋𝐴 −𝑟𝐴′ PBR
=
𝑑𝑊 𝐹𝐴0
Rate law −𝑟𝐴 ′ = 𝑘𝐶𝐴 2 2nd order

Stoichiometry 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 ) Const. volume

Combine 𝑑𝑋𝐴 𝑘 𝐶𝐴0 2 1 − 𝑋𝐴 2 FA0 = CA0 v0

=
𝑑𝑊 𝐹𝐴0
𝑊 𝑋𝐴
Evaluate 𝐹𝐴0 𝑑𝑋𝐴 𝐹𝐴0 𝑋𝐴
Liquid-phase
𝑊 = න 𝑑𝑊 = න = 2nd order reaction
2
𝑘 𝐶𝐴0 1 − 𝑋𝐴 2
𝑘 𝐶𝐴0 2 1 − 𝑋𝐴 PBR
0 0

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Pressure Drop in PBR
• Pressure drop (Δp) is ignored for liquid-phase
kinetics calculations.
• In gas-phase reactions, the concentration of
reactants is proportional to the total pressure.
• Δp can limit the output and conversion for gas-
phase reactions in microreactors.
• For gas-phase reactions, the differential form of
the mole balance must be used to account for Δp.
• When Δp is significant, the ratio of pressure (P/P0)
must be determined as a function of the PFR
reactor volume (V) or the PBR catalyst weight (W).

AI photo for pressure drop in PBR

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 • Second order reaction (2𝐴→𝐵)
• Gas phase
Pressure Drop in PBR •
•
Isothermal
Δp≠0
Calculate catalyst weight (W) required to get XA

Step Equation Remark

Mole balance 𝑑𝑋 PBR
𝐹𝐴0 = −𝑟𝐴 ′
𝑑𝑊
Rate law −𝑟𝐴 ′ = 𝑘𝐶𝐴 2 2nd order

Stoichiometry 𝐹𝐴 (1 − 𝑋𝐴 ) 𝑃 𝑇0 Isothermal (T=T0 )

𝐶𝐴 = = 𝐶𝐴0 Variable volume
𝑣 (1 + 𝜀𝑋) 𝑃0 𝑇 𝑃0 𝑇
𝜐 = 𝜐0 (1 + 𝜀𝑋)
𝑃 𝑇0
2 2 find (P/P0) as f(W)
𝑑𝑋 𝑘𝐶𝐴0 1−𝑋 2 𝑃
Combine =
𝑑𝑊 𝐹𝐴0 1 + 𝜀𝑋 2 𝑃0
Evaluate W=f(X,P)
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Ergun Equation
Pressure Drop in PBR

• The most common eq. used to 𝑑𝑃

=
−𝐺 1 − 𝛷 150 1 − 𝛷 𝜇
+ 1.75𝐺
calculate Δp in a packed bed of catalyst 𝑑𝑧 𝜌𝑔𝑐 𝐷𝑝 𝛷 3 𝐷𝑝 𝑇𝑒𝑟𝑚2
is the Ergun Equation 𝑇𝑒𝑟𝑚1

• The eq. can be used to calculate Δp for

both laminar and turbulent flow:
o Term 1 is dominant for laminar flow
o Term 2 is dominant for turbulent flow

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Ergun Equation
Pressure Drop in PBR
• the only parameter that varies 𝑑𝑃
=
−𝐺 1−𝛷 150 1 − 𝛷 𝜇
+ 1.75𝐺 P
with pressure on the right-hand 𝑑𝑧 𝝆𝑔𝑐 𝐷𝑝 𝛷3 𝐷𝑝 𝑇𝑒𝑟𝑚2
𝑇𝑒𝑟𝑚1
side of Equation is the gas
density • 𝑚ሶ = 𝑚ሶ 0
• 𝜌𝜐 = 𝜌0 𝜐0
• Because the PBR is operated at
steady state, the mass flow rate • 𝜌 = 𝜌0 𝜐
𝜐0
Z W
at any point down the reactor, 𝐹 𝑃 𝑇
• 𝜐 = 𝜐0 𝑇 0
(kg/s), is equal to the entering 𝐹𝑇0 𝑃 𝑇0
mass flow rate 𝑃 𝑇
• 𝜐 = 𝜐0 (1 + 𝜀𝑋) 0
𝑃 𝑇 0

𝐹𝑇0 𝑃 𝑇0
• 𝜌 = 𝜌0
𝐹𝑇 𝑃0 𝑇 P0

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Ergun Equation
Pressure Drop in PBR
𝑑𝑃 −𝐺 1−𝛷 150 1−𝛷 𝜇
• = + 1.75𝐺 P
𝑑𝑧 𝝆𝑔𝑐 𝐷𝑝 𝛷3 𝐷𝑝
𝑇𝑒𝑟𝑚2
𝑇𝑒𝑟𝑚1
𝑑𝑃 −𝐺 1−𝛷 150 1−𝛷 𝜇
• = 𝐹 𝑃𝑇 3 + 1.75𝐺
𝑑𝑧 𝜌0 𝐹𝑇0 𝑃 𝑇0 𝑔𝑐 𝐷𝑝 𝛷 𝐷𝑝
𝑇 0
Z W
𝑑𝑃 −𝐺 1−𝛷 150 1−𝛷 𝜇 𝑃0 𝑇 𝐹𝑇
• = + 1.75𝐺
𝑑𝑧 𝝆𝟎 𝑔𝑐 𝐷𝑝 𝛷3 𝐷𝑝 𝑃 𝑇0 𝐹𝑇0

𝐺 1−𝛷 150 1−𝛷 𝜇

• 𝛽0 = + 1.75𝐺
𝜌0 𝑔𝑐 𝐷𝑝 𝛷3 𝐷𝑝
𝑑𝑃 𝑃0 𝑇 𝐹𝑇
• = −𝛽0 P0
𝑑𝑧 𝑃 𝑇0 𝐹𝑇0

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Ergun Equation
Pressure Drop in PBR
𝑑𝑃 𝑃0 𝑇 𝐹𝑇
• = −𝛽0 P
𝑑𝑧 𝑃 𝑇0 𝐹𝑇0

• Catalyst Weight:
• 𝑾 = 𝑽𝝆𝒃 = (𝒛𝑨𝒄 )𝝆𝒄 (𝟏 − ∅)
• 𝒅𝑾 = 𝑨𝒄 𝝆𝒄 𝟏 − ∅ 𝒅𝒛 ⟹ 𝒅𝒛 = 𝒅𝑾/[𝑨𝒄 𝝆𝒄 𝟏 − ∅ ]
▪ 𝑏𝑢𝑙𝑘 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 = 𝜌𝑏 = 𝜌𝑐 (1 − 𝛷) Z W
▪ 𝑠𝑜𝑙𝑖𝑑 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 = 𝜌𝑐
▪ 𝑝𝑜𝑟𝑜𝑠𝑖𝑡𝑦 (𝑣𝑜𝑖𝑑 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛) = ∅
▪ 𝑠𝑜𝑙𝑖𝑑 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 = 1 − ∅
• For multiple reactions and membrane reactors:
𝑑𝑃 −𝛽0 𝑃0 𝑇 𝐹𝑇
• = P0
𝑑𝑾 𝐴𝑐 1−𝛷 𝜌𝑐 𝑃 𝑇0 𝐹𝑇0
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Ergun Equation
Pressure Drop in PBR
𝑑𝑃 −𝛽0 𝑃0 𝑇 𝐹𝑇 • for single reactions: P
=
𝑑𝑾 𝐴𝑐 1 − 𝛷 𝜌𝑐 𝑃 𝑇0 𝐹𝑇0 𝑑𝑝 𝛼1 𝑇
=− 1 + 𝜀𝑋
Let: 𝑑𝑊 2 𝑝 𝑇0

• 𝜶=
𝟐𝜷𝟎 𝟏 • Isothermal case:
𝑨𝒄 𝟏−𝜱 𝝆𝒄 𝑷𝟎
𝑑𝑝 𝛼1
• 𝑝=
𝑃
𝑑𝑊
=−
2𝑝
1 + 𝜀𝑋 Z W
𝑃0
𝑑𝑝 ∝ 𝑇 𝐹𝑇
• =
𝑑𝑊 2𝑝 𝑇0 𝐹𝑇0

• We will use this form for single reactions:

𝑑 𝑃Τ𝑃0 𝛼 1 𝑇
• =− 1 + 𝜀𝑋 P0
𝑑𝑊 2 𝑃Τ𝑃0 𝑇0

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Ergun Equation
Pressure Drop in PBR
• These two expressions are coupled ordinary 𝑑𝑋 2
𝑘𝐶𝐴0 (1−𝑋)2 2 P
differential equations (ODEs) • = 𝑝
𝑑𝑊 𝐹𝐴0 (1+𝜀𝑋)2
• We can only solve them simultaneously using 𝑑𝑝 𝛼1
• = − 1 + 𝜀𝑋
an ODE solver such as Polymath to get X and p 𝑑𝑊 2𝑝
at a certain W used.
• For the special case of isothermal operation Z W
and epsilon ε = 0, we can obtain an analytical
solution.
• Polymath will combine the Mole Balances,
Rate Laws and Stoichiometry.
P0
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Ergun Equation
Pressure Drop in PBR
Analytical solution ( special case) 𝑑𝑝 −𝛼 𝑑𝑝
• = ⟹ − 𝛼 = 2𝑝 P
𝑑𝑊 2𝑝 𝑑𝑊
• Isothermal
• relocating 𝑝 inside derivative
• No expansion (ε = 0 )
𝑑𝑝2 = −𝛼𝑑𝑊
• Integrating with 𝑝 =1 (P=P0) at
2𝛽0 1 Z W
• 𝛼= W=0
𝐴𝑐 1−𝜑 𝜌𝑐 𝑃0
𝑝2 = (1 − 𝛼𝑊)
𝐺 1−𝛷 150 1−𝛷 𝜇
• 𝛽0 = 𝜌 𝛷3
+ 1.75𝐺
0 𝑔𝑐 𝐷𝑝
𝒑 = (𝟏 − 𝜶𝑾)𝟏/𝟐
𝐷𝑝

P0
4/14/2024 12
Effect of pressure drop in a PBR
qualitatively the effects of pressure drop on reactor design.

Pressure Drop Concentration Profile

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Effect of pressure drop in a PBR
qualitatively the effects of pressure drop on reactor design.

Reaction rate Conversion

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Effect of pressure drop in a PBR
qualitatively the effects of pressure drop on reactor design.

Volumetric flow rate

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 • 2nd order reaction (2𝐴→𝐵)
• Gas phase
Pressure Drop in PBR • Isothermal
• No expansion (𝜀 = 0)
• Δp≠0
Step Equation Remark
Mole balance 𝑑𝑋 𝑃
𝐹𝐴0 = −𝑟𝐴 ′ = (1 − 𝛼𝑊)1/2
𝑑𝑊 𝑃0
Rate law −𝑟𝐴 ′ = 𝑘𝐶𝐴 2 (no pressure drop means α=0)
Stoichiometry 𝐹𝐴 (1 − 𝑋𝐴 ) 𝑃 𝑇 𝑊 = 𝑉𝜌𝑏 = (𝑧𝐴𝑐 )𝜌𝑐 (1 − ∅)
𝐶𝐴 = = 𝐶𝐴0
𝑣 (1 + 𝜀𝑋) 𝑃0 𝑇0 2𝛽0 1
2 2 2 𝛼=
𝑑𝑋 𝑘𝐶𝐴0
1−𝑋 𝑃 𝐴𝑐 1 − 𝜑 𝜌𝑐 𝑃0
Combine = 2 𝐺 1−𝛷 150 1 − 𝛷 𝜇
𝑑𝑊 𝐹𝐴0 1 + 𝜀𝑋 𝑃0 𝛽0 = + 1.75𝐺
𝜌0 𝑔𝑐 𝐷𝑝 𝛷 3 𝐷𝑝

Evaluate 𝑘𝐶𝐴0 𝑊 𝛼𝑊
1− 1Τ2
ν0 2 1 − 1 − (2ν0 𝛼)Τ𝑘𝐶𝐴0 𝑋𝐴 /(1 − 𝑋𝐴 )
𝑋𝐴 = 𝑊=
𝑘𝐶 𝑊 𝛼𝑊 α
1 + 𝐴0 1−
4/14/2024 ν0 2 16
Example 5-5 Effect of Pressure Drop on the
Conversion Profile
Consider the PBR for a The flow and packed-bed conditions are:
P
second order reaction: • P0 = 10 atm = 1013 kPa
• Entering volumetric flow rate: υ0 = 7.15 m3 Τh
2A → B + C • The entering concentration of A = CA0 =0.1
a) Calculate the kmol/m3
12𝑚6
conversion in the • the specific reaction rate is 𝑘 = W
𝑘𝑚𝑜𝑙∙𝑘𝑔−𝑐𝑎𝑡∙ℎ
Z
absence of pressure • Catalyst pellet size: Dp = 0.006 m
drop. • catalyst density: ρc = 1923 kgΤm3
b) Calculate the • void fraction=0.45
conversion accounting • Cross − sectional area: Ac = 0.0013 m2
• Pressure drop parameter: β0 = 25.8 kPaΤm
for pressure drop.
• Reactor length: L = 20 m P0
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Example 5-5 Effect of Pressure Drop on the
Conversion Profile
• Equation for the conversion: • The weight of the catalyst:
𝑊 = 𝐴𝑐 𝜌𝑏 𝐿
𝑘𝐶𝐴0 𝑊 𝛼𝑊
1− 𝑊 = 0.0013 𝑚2 1058 𝑘𝑔Τ𝑚3 20 𝑚
υ0 2
𝑋= 𝑊 = 27.5 𝑘𝑔
𝑘𝐶 𝑊 𝛼𝑊
1 + 𝐴0 1−
υ0 2 • the bulk catalyst density:
𝑊 12𝑚6 𝑘𝑚𝑜𝑙 27.5 𝑘𝑔
• 𝑘𝐶𝐴0 = 0.1 𝜌𝑏 = 𝜌𝑐 1 − ∅
υ0 𝑘𝑚𝑜𝑙∙𝑘𝑔−𝑐𝑎𝑡∙ℎ 𝑚3 7.15 𝑚3 Τℎ
𝑊 𝜌𝑏 = 1923 1 − 0.45
𝑘𝐶𝐴0 = 4.6
υ0 𝜌𝑏 = 1058 𝑘𝑔Τ𝑚3

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Example 5-5 Effect of Pressure Drop on the Conversion Profile

a) conversion in the absence of pressure b) conversion accounting for pressure

drop drop
no pressure drop ⟹ α=0: • Calculate 𝛼 , as there is pressure drop
𝑘𝐶𝐴0 𝑊 𝛼𝑊 2𝛽0
υ0
1− 2 • 𝛼= = 0.037 𝑘𝑔−1
• 𝑋= 𝑘𝐶𝐴0 𝑊 𝛼𝑊
𝐴𝑐 𝜌𝑐 1−∅ 𝑃0
1+ 1−
υ0 2
𝛼𝑊 0.037 27.5
• Substitute: α=0 • 1− =1− = 0.49
2 2

𝑘𝐶𝐴0 𝑊 𝑘𝐶𝐴0 𝑊 𝛼𝑊
υ0
1− 2 (4.6)(0.49)
4.6
• 𝑋=
υ0
= = 0.82 • 𝑋= 𝑘𝐶 𝑊 𝛼𝑊 =
𝑘𝐶𝐴0 𝑊 1+4.6 1+ υ𝐴0 1− 2 1+(4.6)(0.49)
1+ υ 0
0

• 𝑋 = 0.82 • 𝑋 = 0.693

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 Week 9 / Lecture 2

CH.6. ISOTHERMAL REACTOR DESIGN: MOLES AND

MOLAR FLOW RATE
• Molar flow rate balance and rate law
• Mole balances on CSTR, PFR, and batch reactors
• Microreactors
• Membrane reactors
4/14/2024 20
 • 2nd order reaction (2𝐴→𝐵)
• Gas phase
Pressure Drop in PBR • Isothermal Recall
• No expansion (𝜀 = 0)
• Δp≠0
Step Equation Remark
Mole balance 𝑑𝑋 𝑃
𝐹𝐴0 = −𝑟𝐴 ′ = (1 − 𝛼𝑊)1/2
𝑑𝑊 𝑃0
Rate law −𝑟𝐴 ′ = 𝑘𝐶𝐴 2 (no pressure drop means α=0)
Stoichiometry 𝐹𝐴 (1 − 𝑋𝐴 ) 𝑃 𝑇 𝑊 = 𝑉𝜌𝑏 = (𝑧𝐴𝑐 )𝜌𝑐 (1 − ∅)
𝐶𝐴 = = 𝐶𝐴0
𝑣 (1 + 𝜀𝑋) 𝑃0 𝑇0 2𝛽0 1
2 2 2 𝛼=
𝑑𝑋 𝑘𝐶𝐴0
1−𝑋 𝑃 𝐴𝑐 1 − 𝜑 𝜌𝑐 𝑃0
Combine = 2 𝐺 1−𝛷 150 1 − 𝛷 𝜇
𝑑𝑊 𝐹𝐴0 1 + 𝜀𝑋 𝑃0 𝛽0 = + 1.75𝐺
𝜌0 𝑔𝑐 𝐷𝑝 𝛷 3 𝐷𝑝

Evaluate 𝑘𝐶𝐴0 𝑊 𝛼𝑊
1− 1Τ2
ν0 2 1 − 1 − (2ν0 𝛼)Τ𝑘𝐶𝐴0 𝑋𝐴 /(1 − 𝑋𝐴 )
𝑋𝐴 = 𝑊=
𝑘𝐶 𝑊 𝛼𝑊 α
1 + 𝐴0 1−
4/14/2024 ν0 2 21
Introduction
• Writing mole balances in terms of conversion Mole Balance
(X) is effective for single reactions.
• It is convenient to write mole balances in Relative
Rate Law
terms of moles (N) or molar flow rates (F) for Rates
multiple reactions.
Stoichiometry
Pressure
• The algorithm can be changed to analyze Drop
these situations.
• Molar flow rates will be used to analyze a Combine

microreactor, a membrane reactor, and a

semibatch reactor. Evaluate

4/14/2024 22
 • CSTRs
Mole Balances • PFRs • Isothermal-reaction design algorithm
• PBRs • Mole balances (𝑨 + 𝟐𝑩 ⇌ 𝒄)
• BR

Step Equation Remark

1) Mole Balance PFR PBR
on each species 𝑑𝐹𝐴 𝑑𝐹𝐵 𝑑𝐹𝐶 𝑑𝐹𝐴 ′ 𝑑𝐹𝐵 𝑑𝐹𝐶
= 𝑟𝐴 , = 𝑟𝐵 , = 𝑟𝐶 = 𝑟𝐴 , = 𝑟𝐵
′
, = 𝑟𝐶′
𝑑𝑉 𝑑𝑉 𝑑𝑉 𝑑𝑊 𝑑𝑊 𝑑𝑊
2) Rate Law 𝐶𝐶
in terms of Conc. −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵2 −
𝐾𝐶
Relative Rates −𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐵 = 2𝑟𝐴 , 𝑟𝐶 = −𝑟𝐴
= =
Of each species to one another 1 2 1
3) Stoichiometry For gas reactions: For batch or liquid reactions,
𝐹 𝑇 𝑃 use concentration, 𝐶𝐴 , 𝐶𝐵
𝐶𝐴 = 𝐶𝑇0 𝐹 𝐴 𝑇0 𝑃 ; 𝐹𝑇 = 𝐹𝐴 + 𝐹𝐵 + 𝐹𝐶
𝑇0 0

Pressure Drop 𝑑𝑝 𝛼 𝑇 𝐹𝑇 𝑃
=− 𝑝=
Gas phase reactions in terms of 𝑑𝑊 2𝑝 𝑇0 𝐹𝑇0 𝑃0
molar flow rates
4) Combine For isothermal operation, T = T0, use an ODE solver or a nonlinear equation
5) Evaluate solver (e.g., Polymath) to combine previous Steps to solve for, the profiles of
molar flow rates, concentration, and pressure.
4/14/2024 23
 • CSTRs
Mole Balances •
•
PFRs
PBRs
Liquid Phase • BR

4/14/2024 24
 • CSTRs
Mole Balances •
•
PFRs
PBRs
• Isothermal-reaction design algorithm
• Mole balances (𝐚𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫)
Gas Phase • BR

Step Equation
1) Mole Balance

4/14/2024 25
 • CSTRs
Mole Balances •
•
PFRs
PBRs
• Isothermal-reaction design algorithm
• Mole balances (𝐚𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫)
Gas Phase • BR

2) Rate Law 𝛽
−𝑟𝐴′ = 𝑘𝐴 𝐶𝐴𝛼 𝐶𝐵

Relative Rates −𝑟𝐴′ −𝑟𝐵′ −𝑟𝐶′ −𝑟𝐷′

= = =
−𝑎 −𝑏 −𝑐 −𝑑
𝑏 𝑐 𝑑
𝑟𝐵′ = 𝑟𝐴′ 𝑟𝐶′ = − 𝑟𝐴′ 𝑟𝐷′ = − 𝑟𝐴′
𝑎 𝑎 𝑎
3) Stoichiometry Concentrations
𝐹 𝑇0 𝐹 𝑇0 𝐹 𝑇0 𝐹 𝑇0
𝐶𝐴 = 𝐶𝑇0 𝐹𝐴 𝑝 , 𝐶𝐵 = 𝐶𝑇0 𝐹𝐵 𝑝 , 𝐶𝐶 = 𝐶𝑇0 𝐹𝐶 𝑝 , 𝐶𝐷 = 𝐶𝑇0 𝐹𝐷 𝑝
𝑇 𝑇 𝑇 𝑇 𝑇 𝑇 𝑇 𝑇

𝐹𝑇 = 𝐹𝐴 + 𝐹𝐵 + 𝐹𝐶 + 𝐹𝐷 + 𝐹𝐼
Pressure Drop 𝑑𝑝 −∝ 𝐹𝑇 𝑇 𝑃
= , 𝑝=
𝑑𝑊 2𝑝 𝐹𝑇0 𝑇0 𝑃0

4) Combine Combine steps 1 to 3. (Many times we will let the ODE solver replace Step 4, Combine)
5) Evaluate • Specify and enter parameter values: 𝑘𝐴 , 𝐶𝑇0 , ∝, 𝛽, 𝑇0 , 𝑎, 𝑏, 𝑐, 𝑑
• Specify and enter molar flow rates: 𝐹𝐴0 , 𝐹𝐵0 , 𝐹𝐶0 , 𝐹𝐷0 , 𝑎𝑛𝑑 𝑉𝑓𝑖𝑛𝑎𝑙
4/14/2024 26
Application of the PFR Molar Flow Rate
Microreactor
Attributes
• Small-scale chemical reactors
• High surface-to-volume ratios
• Improved heat and mass transfer
• Enhanced selectivity and yield
• Reduced reaction times
Microreactors to produce nitroglycerine
• Improved safety Microreactors safely produce highly unstable
liquid explosives with minimal damage per unit
due to small material quantities.
• Reduced environmental impact

4/14/2024 27
Application of the PFR Molar Flow Rate
Microreactor
Applications
• pharmaceutical synthesis
Microreactor
• fine chemical synthesis
• catalysis
• nanotechnology
• materials science
Microplant

• energy production

4/14/2024 28
Membrane Reactors
• Catalytic membrane reactors save 10
trillion Btu/year vs. conventional ones
for dehydrogenation.
• Membranes push conversions past
equilibrium in thermodynamically
limited reactions.
• By applying Le Chatelier’s principle,
removing products drives reactions
forward.
• Using a selectively permeable
membrane around the mixture
achieves this.
4/14/2024 29
Membrane Reactors
• The membrane can selectively block or allow
substances, shield catalysts from unwanted
contact, or function as a catalyst with
reactive sites.
• Applications
• Hydrogen production
• Methanol production
• Water desalination
• Air separation commercial ceramic membranes
• Carbon dioxide capture and storage

4/14/2024 30
Types of Membrane Reactors

IMRCF CMR
• Inert Membrane Reactor with Catalyst • Catalytic Membrane Reactor
Pellets on the Feed Side • The catalyst is deposited directly on the
• The membrane is inert and serves as a membrane, and only specific reaction
barrier to the reactants and some of the products are able to exit the permeate
products side

4/14/2024
𝐶6 𝐻12 ↔ 3𝐻2 + 𝐶6 𝐻6 31
Mole Balance on Membrane Reactors
• In analyzing the membrane reactors, 𝐶6 𝐻12 ↔ 3𝐻2 + 𝐶6 𝐻6
we only need to make a small change 𝐴 ↔ 3𝐵 + 𝐶
to the algorithm
• Choose the reactor volume rather
than catalyst weight as an
independent variable
• The mole balances on the chemical
species that stay within the reactor: A
and C

Schematic of IMRCF for mole balance

4/14/2024 32
Mole Balance on Membrane Reactors
• A - Balance:
𝐼𝑛 𝑏𝑦 𝑓𝑙𝑜𝑤 𝑂𝑢𝑡 𝑏𝑦 𝑓𝑙𝑜𝑤 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
ฑ
𝐹𝐴ȁ𝑉 − 𝐹𝐴ȁ𝑉+∆𝑉 + 𝑟ฑ 𝐴 ∆𝑉 = ฎ
0
𝑑𝐹𝐴
= 𝑟𝐴
𝑑𝑉
• C - Balance (identical manner to A)
𝑑𝐹𝐶
= 𝑟𝐶
𝑑𝑉

4/14/2024 33
Mole Balance on Membrane Reactors
• B - Balance:
• Mole balance on B (H2) must be modified as (H2) leaves
through both the sides of the reactor and at the end of
the reactor.
𝐼𝑛 𝑏𝑦 𝑓𝑙𝑜𝑤 𝑂𝑢𝑡 𝑏𝑦 𝑓𝑙𝑜𝑤 𝑂𝑢𝑡 𝑏𝑦 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
• ฑ
𝐹𝐵 ȁ𝑉 − 𝐹𝐵ȁ𝑉+∆𝑉 − 𝑅𝐵 ∆𝑉 + 𝑟𝐵 ∆𝑉 = ฎ
0
• RB is the molar flow rate of B leaving through the sides of the reactor.
• Dividing by ΔV and taking the limit as ΔV → 0
𝑑𝐹𝐵
• = 𝑟𝐵 − 𝑅𝐵
𝑑𝑉
moles of B through sides
• 𝑅𝐵 =
volume of reactor

4/14/2024 34
Mole Balance on Membrane Reactors
• B - Balance: • 𝑅𝐵 : Rate of B out through
the side
• Flux through the membrane:
• 𝑊𝐵 : molar flux of B normal
molar flow rate through membrane 𝑚𝑜𝑙 to the membrane (sides of
• 𝑊𝐵 = 𝑘𝐶′ (𝐶𝐵 − 𝐶𝐵𝑆 ) =
surface area of membrane 𝑚2 ⋅𝑠 reactor), (mol/m2/s)
• 𝑅𝐵 = 𝑊𝐵 𝑎 = 𝑘𝐶′ 𝑎 𝐶𝐵 − 𝐶𝐵𝑆 • kc’: overall mass transfer
membrane surface area 𝜋𝐷𝐿 4 𝑚2 coefficient in m/s
• 𝑎= = 𝜋𝐷2 =
reactor volume 𝐿 𝐷 𝑚3
• kC in s-1.
4

• 𝑘𝐶 = 𝑘𝐶′ 𝑎 • CBS: concentration of B in

the sweep gas channel
𝑚𝑜𝑙
• 𝑅𝐵 = 𝑘𝐶 𝐶𝐵 − 𝐶𝐵𝑆 (mol/m3). Often neglected
𝑚3 ⋅𝑠

4/14/2024 35
Example 6–2 Membrane Reactor
• Propane dehydrogenation thrives in a membrane • Gas-solid catalytic reaction info: Use bulk catalyst density
reactor. for balances in terms of reactor volume ( –rA=-rA’ρb)
• Bulk catalyst density: 1.5 g/cm3.
C3H8 ↔ C3H6 + H2
• Tube: 2-cm inside-diameter with catalyst pellets.
• Dehydrogenation reactions, symbolized as
A ↔ B+C, happen on the catalyst side of an IMRCF. • Specific reaction rate (k): 0.7 min-1

• KC for this reaction at 227 °C is small (e.g., KC = 0.05 • Transport coefficient (kC): 0.2 min-1
mol/L). Required:
• The membrane permits passage of B (H2) but not A a) Perform differential mole balances on A, B, and
and C. C to arrive at a set of coupled differential
• Gaseous A enters at 8.2 atm and 227C (CT0 = 0.2 equations to solve.
mol/L) with a flow rate of 10 mol/min. b) Plot and analyze the molar flow rates of each
• RB (B's diffusion rate out of the reactor per unit species as a function of reactor volume.
volume) is proportionate to its concentration c) Calculate the conversion of A at V = 500 L.
(RB = kC CB).

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Example 6–2 Membrane Reactor
• Choose reactor volume over catalyst weight
as the independent variable.
• Catalyst weight (W) and reactor volume (V)
relate via bulk catalyst density: (W = ρb V).
• Perform mole balances on the volume
element ΔV shown in Figure

4/14/2024 37
Example 6–2 Membrane Reactor
A ↔ B+C
Step Equation
1) Mole Balance 𝑖𝑛 𝑓𝑙𝑜𝑤 − 𝑜𝑢𝑡 𝑓𝑙𝑜𝑤 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
A-Balance, C-Balance
𝑑𝐹𝐴 𝑑𝐹𝐶
= 𝑟𝐴 , = 𝑟𝐶
𝑑𝑉 𝑑𝑉
B-Balance
𝑑𝐹𝐵
= 𝑟𝐵 − 𝑅𝐵
𝑑𝑉
2) Rates 𝐶𝐵 𝐶𝐶
−𝑟𝐴 = 𝑘 𝐶𝐴 −
𝐾𝐶
Relative Rate 𝑟𝐴 𝑟𝐵 𝑟𝐶
= =
−1 +1 +1
𝑟𝐵 = −𝑟𝐴
4/14/2024 𝑟𝐶 = −𝑟𝐴 38
Example 6–2 Membrane Reactor
Transport out of the Concentration of B of the sweep side is zero, CBS = 0
reactor 𝑅𝐵 = 𝑘𝐶 𝐶𝐵

3) Stoichiometry for the case of constant temperature (T=T0) and constant pressure (P=P0)
Concentrations:
𝐹 𝐹 𝐹
𝐶𝐴 = 𝐶𝑇0 𝐹𝐴 𝐶𝐵 = 𝐶𝑇0 𝐹𝐵 𝐶𝐶 = 𝐶𝑇0 𝐹𝐶
𝑇 𝑇 𝑇
𝐹𝑇 = 𝐹𝐴 + 𝐹𝐵 + 𝐹𝐶

4) Combining 𝑑𝐹𝐴 𝑑𝐹𝐶

= 𝑟𝐴 , = 𝑟𝐶
𝑑𝑉 𝑑𝑉
𝑑𝐹𝐵 𝐹𝐵
= 𝑟𝐵 − 𝑅𝐵 = −𝑟𝐴 − 𝑘𝐶 𝐶𝐵 = −𝑟𝐴 − 𝑘𝐶 𝐶𝑇0
𝑑𝑉 𝐹𝑇
𝐹𝐴 𝐶𝑇0 𝐹𝐵 𝐹𝐶
−𝑟𝐴 = 𝑘𝐶𝑇0 −
𝐹𝑇 𝐾𝐶 𝐹𝑇 𝐹𝑇
𝐹𝑇 = 𝐹𝐴 + 𝐹𝐵 + 𝐹𝐶

4/14/2024 39
Example 6–2 Membrane Reactor
5) Evaluation 𝑃0 830.6 𝑘𝑃𝑎
𝐶𝑇0 = = = 0.2 𝑚𝑜𝑙/𝐿
𝑅𝑇0 [8.314 𝐾 𝑃𝑎 𝐿 ](500 𝐾)
𝑚𝑜𝑙 𝐾
−1
𝑚𝑜𝑙
𝑘 = 0.7𝑚𝑖𝑛 , 𝐾𝐶 = 0.05 , 𝑘𝐶 = 0.2𝑚𝑖𝑛−1
𝐿
𝐹𝐴0 = 10 𝑚𝑜𝑙/𝑚𝑖𝑛
𝐹𝐵0 = 𝐹𝐶0 = 0
Numerical Solution
(Polymath)

Entering conditions at V=0

• FA=FA0
• FB=FC=0

4/14/2024 40
 Example 6–2 Membrane Reactor
Analysis
• FA at V=500 L is 4 mol/min
• FA drops rapidly until about 100 L, where the reaction
approaches equilibrium.
• FB goes through a max due to the competition
between the rate of B formation and removal.
• The reaction will only proceed to the right at the rate
at which B is removed through the sides of the
membrane, as noted by the similar slopes of FA and
FB in the plot.
• If B is removed rapidly, FB will close to zero and the
reaction behaves as if it is irreversible.
• If B is removed slowly, FB will be large throughout the
reactor and the rate of reaction, -rA, will be small. 𝐹𝐴0 − 𝐹𝐴 10 − 4
𝑋= = = 0.6
𝐹𝐴0 10
4/14/2024 41
4/14/2024 42