UNIT 12: HETEROGENEOUS CATALYSIS:

DIFFUSION AND REACTION IN POROUS CATALYST

Recommended Reading: HSF Chapter 15.1-15.8

LEARNING OBJECTIVES

◼ Apply mass transfer concepts for pore diffusion limited reactions.

◼ Write rate expression for internal mass transfer limited reactions.
◼ Design packed bed reactor operating under internal mass transfer limited
conditions.

DIFFUSION AND REACTION 2

OUTLINE

◼ Mass Transfer Fundamentals: Pore Diffusion

◼ Pore Diffusion and Reaction
◼ Packed bed reactor design
◼ Reaction rate limiting regimes from experimental data

DIFFUSION AND REACTION 3

MASS TRANSFER FUNDAMENTALS: PORE DIFFUSION
𝐶𝐴 (𝑟)
◼ Pores are tortuous, interconnecting paths with varying
cross-sectional areas.
𝐶𝐴𝑠
◼ Species motion within the pores is purely diffusive.
𝐴
◼ Concentration of species within the pellet depends on
molecular diffusion.
◼ Effective diffusion coefficient (𝐷𝑒 ) is used to describe the
average diffusion within the pellet.
Molar flux of species,
𝑑𝐶𝐴
𝑊𝐴𝑟 = −𝐷𝑒
𝑑𝑟
𝑊𝐴𝑟 is positive in the direction of increasing 𝑟.

What are the factors that affect 𝐷𝑒 ?

DIFFUSION AND REACTION 4

DIFFUSION AND REACTION
➢ Pore diffusion: Species A diffuses from pellet surface to active site
through the pores.
➢ Surface Reaction: At the active sites within the pores.
𝑨⇆𝑹
➢ Pore diffusion: Species R diffuses from active site to pellet surface
through the pores.
Reaction rate varies throughout the pellet and is described by Internal
Effectiveness factor
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
𝜂= 𝐶𝐴𝑠 𝐶𝐴
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑖𝑓 𝑝𝑒𝑙𝑙𝑒𝑡 𝑖𝑛𝑡𝑒𝑟𝑖𝑜𝑟 𝑖𝑠 𝑒𝑥𝑝𝑜𝑠𝑒𝑑 𝑡𝑜 𝐶𝐴𝑠
−𝑟𝐴 −𝑟 ′𝐴 −𝑟 ′′𝐴
𝜂= = =
−𝑟𝐴𝑠 −𝑟 𝐴𝑠 −𝑟 ′′𝐴𝑠
′ 𝐶𝐴 = 𝑓(𝑟)
Reaction rate law (pore diffusion limited conditions)
−𝑟 ′′𝐴 = 𝜂 −𝑟 ′′𝐴𝑠
How to derive 𝜂?
DIFFUSION AND REACTION 5
 −𝑟𝐴 × (𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑒𝑙𝑙𝑒𝑡) 𝑀𝐴
𝜂= =
−𝑟𝐴𝑠 × (𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑒𝑙𝑙𝑒𝑡) 𝑀𝐴𝑠
𝑀𝐴𝑠 : Change in the moles of A due to reaction within the pore when exposed to external conditions
(𝐶𝐴 = 𝐶𝐴𝑠 ).
4 3
𝑀𝐴𝑠 = (−𝑟𝐴𝑠 ) × 𝜋𝑅
3
𝑛 4 3
𝑀𝐴𝑠 = 𝑘𝑛 𝐶𝐴𝑠 × 𝜋𝑅
3
𝑀𝐴 : Change in the moles of A due to reaction within the pore under pore diffusion limited conditions
(𝐶𝐴 = 𝑓(𝑟)).
𝑀𝐴 = −4𝜋𝑅2 𝑊𝐴𝑟 ቚ
𝑟=𝑅

𝑑𝐶𝐴
𝑀𝐴 = −4𝜋𝑅2 −𝐷𝑒 อ
𝑑𝑟
𝑟=𝑅

How to evaluate 𝑑𝐶𝐴 Τ𝑑𝑟?

DIFFUSION AND REACTION 6

a) Evaluation of concentration profile within pellet
Mole Balance
𝐼𝑛 − 𝑂𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
𝐶𝐴𝑠
𝑊𝐴𝑟 4𝜋𝑟 2 ቚ − 𝑊𝐴𝑟 4𝜋𝑟 2 ቚ + 𝑟 ′𝐴 4𝜋𝑟 2 ∆𝑟 𝜌𝑐 = 0 𝑅
𝑟 𝑟+∆𝑟

Dividing by −4𝜋∆𝑟 and setting ∆𝑟 → 0

𝑑
𝑊𝐴𝑟 𝑟 2 − 𝑟 ′𝐴 𝜌𝑐 𝑟 2 = 0 𝑟
𝑑𝑟 𝑟 + ∆𝑟
Molar Flux
𝑑𝐶𝐴 𝑑 𝑑𝐶𝐴 2
𝑊𝐴𝑟 = −𝐷𝑒 −𝐷𝑒 𝑟 + 𝑘′𝑛 𝐶𝐴 𝑛 𝜌𝑐 𝑟 2 = 0
𝑑𝑟 𝑑𝑟 𝑑𝑟
Reaction Kinetics
Reaction Rate Law: −𝑟𝐴 = 𝑘𝑛 𝐶𝐴 𝑛
Reaction Rate in terms of catalyst properties: −𝑟 ′𝐴 = 𝑘′𝑛 𝐶𝐴 𝑛 (or) −𝑟 ′′𝐴 = 𝑘′′𝑛 𝐶𝐴 𝑛

How to rewrite reaction kinetics in terms of 𝑘𝑛 ?

DIFFUSION AND REACTION 7
Relation between reaction rates: −𝑟𝐴 𝑉 = −𝑟 ′𝐴 𝑊 = −𝑟′′𝐴 𝑆
Using the relation, 𝑉: Reaction volume
𝑊 𝑊: Mass of catalyst
−𝑟𝐴 = −𝑟′𝐴 ⟹ −𝑟𝐴 = −𝑟′𝐴 𝜌𝑐
𝑉 𝑆: Interfacial surface area
′
𝑆 ⟹ −𝑟 ′𝐴 = −𝑟′′𝐴 𝑆𝑎 𝜌𝑐 : Density of catalyst
−𝑟 𝐴 = −𝑟′′𝐴
𝑊 𝑆𝑎 : Surface area per unit mass of catalyst

Relation between reaction rate constants: 𝑘𝑛 = 𝑘′𝑛 𝜌𝑐 = 𝑘′′𝑛 𝜌𝑐 𝑆𝑎

Using the above,
𝑑𝑑 𝑑𝐶
𝑑𝐶𝐴𝐴 22 𝑛
−𝐷 𝑟 + 𝑘′ 𝐶 𝑛𝜌 2𝑟 2 = 0
𝑑𝑟 −𝐷𝑒𝑒
𝑑𝑟 𝑟 + 𝑘𝑛𝑛 𝐴 𝑟𝑐 = 0
𝐶𝐴
𝑑𝑟 𝑑𝑟
Simplifying,
𝑑 2 𝐶𝐴 2 𝑑𝐶𝐴 𝑘𝑛 𝑛
+ − 𝐶 =0
𝑑𝑟 2 𝑟 𝑑𝑟 𝐷𝑒 𝐴
Dimensionless form of the above equation can be obtained…..

DIFFUSION AND REACTION 8

Using, 𝑑 2 𝜓 2 𝑑𝜓 𝑘𝑛 𝑅2 𝐶𝐴𝑠 𝑛−1 𝑛
𝐶𝐴 𝑟 2
+ − 𝜓 =0
𝜓= 𝜆= 𝑑𝜆 𝜆 𝑑𝜆 𝐷𝑒
𝐶𝐴𝑠 𝑅
𝑑 2 𝜓 2 𝑑𝜓 2 𝑛
+ − 𝜙 𝑛 𝜓 =0
𝑑𝜆2 𝜆 𝑑𝜆
2 𝑛−1
𝑘 𝑛 𝑅 𝐶𝐴𝑠
𝜙𝑛 2 = Thiele Modulus
𝐷𝑒
𝑛
𝑘 𝑛 𝑅𝐶 𝐴𝑠 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
𝜙𝑛 2 = =
𝐷𝑒 /𝑅(𝐶𝐴𝑠 − 0) 𝐼𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
Reaction Rate Law: −𝑟𝐴 = 𝑘1 𝐶𝐴 (or) −𝑟′′𝐴 = 𝑘′′1 𝐶𝐴
𝑘1 𝑅2 𝑘′′1 𝜌𝑐 𝑆𝑎 𝑅2
𝜙1 2 = 𝑜𝑟 𝜙1 2 =
𝐷𝑒 𝐷𝑒
What if 𝜙𝑛 ≫?

What if 𝜙𝑛 ≪?

DIFFUSION AND REACTION 9

Writing the differential equation for a first order reaction,
𝑑 2 𝜓 2 𝑑𝜓 2
+ − 𝜙1 𝜓=0
𝑑𝜆2 𝜆 𝑑𝜆
Solution for the differential equation is possible using appropriate boundary conditions.
Boundary Conditions
𝑟=0 𝐶𝐴 = 𝑓𝑖𝑛𝑖𝑡𝑒
𝑟=𝑅 𝐶𝐴 = 𝐶𝐴𝑠
𝐶𝐴𝑠
(or) 𝑅

𝜆=0 𝜓 = 𝑓𝑖𝑛𝑖𝑡𝑒
𝜆=1 𝜓=1
𝑟
Solving, 𝑟 + ∆𝑟
𝐶𝐴 1 𝑠𝑖𝑛ℎ𝜙1 𝜆 1 𝑥
𝜓= = 𝑠𝑖𝑛ℎ𝑥 = 𝑒 − 𝑒 −𝑥
𝐶𝐴𝑠 𝜆 𝑠𝑖𝑛ℎ𝜙1 2

Concentration profile of species A in a porous pellet (first order reaction)

DIFFUSION AND REACTION 10

 Concentration profile for different values of Thiele Modulus (𝜙1 )
Which of the plots corresponds to large and small values of Thiele Modulus?
Why?

𝐶𝐴
𝜓=
𝐶𝐴𝑠

𝑟
𝜆=
𝑅

DIFFUSION AND REACTION 11

b) Change in moles of A (Pellet interior same as external surface condition)
4
𝑀𝐴𝑠 = (−𝑟𝐴𝑠 ) × 𝜋𝑅3
3
For first order reaction,
4 3
𝑀𝐴𝑠 = 𝑘1 𝐶𝐴𝑠 × 𝜋𝑅
3
c) Change in moles of A (Pore diffusion limiting condition)
𝑀𝐴 = −4𝜋𝑅2 𝑊𝐴𝑟 ቚ
𝑟=𝑅
𝑑𝐶𝐴
𝑀𝐴 = −4𝜋𝑅2 −𝐷𝑒 อ
𝑑𝑟
𝑟=𝑅

Using,
𝑑𝐶𝐴 𝐶𝐴𝑠 𝑑𝜓
=
𝑑𝑟 𝑅 𝑑𝜆
𝑑𝜓
𝑀𝐴 = 4𝜋𝑅𝐶𝐴𝑠 𝐷𝑒 อ
𝑑𝜆
𝜆=1
DIFFUSION AND REACTION 12
Concentration profile of species A within the pores (first order reaction)
1 𝑠𝑖𝑛ℎ𝜙1 𝜆
𝜓=
𝜆 𝑠𝑖𝑛ℎ𝜙1
Differentiate the above w.r.t 𝜆 and set 𝜆 = 1,
𝑑𝜓
อ = 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1
𝑑𝜆
𝜆=1

Using the above,

𝑀𝐴 = 4𝜋𝑅𝐶𝐴𝑠 𝐷𝑒 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1
d) Internal effectiveness factor
−𝑟𝐴 × (𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑒𝑙𝑙𝑒𝑡) 𝑀𝐴
𝜂= =
−𝑟𝐴𝑠 × (𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑒𝑙𝑙𝑒𝑡) 𝑀𝐴𝑠
4𝜋𝑅𝐶𝐴𝑠 𝐷𝑒 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1
𝜂=
4
𝑘1 𝐶𝐴𝑠 × 𝜋𝑅3
3
𝑘1
3 𝜙1 = 𝑅
𝜂 = 2 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1 𝐷𝑒
𝜙1
DIFFUSION AND REACTION 13
 Effectiveness factor (𝜂) versus Thiele Modulus (𝜙1 ) for first order reaction

3
𝜂= 2 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1
𝜙1

𝑘1 𝑘′′1 𝑆𝑎 𝜌𝑐
𝜙1 = 𝑅 =𝑅
𝐷𝑒 𝐷𝑒

Effect of particle diameter?

Small R:
Large R:

Diffusion Limited condition,

𝜙1 > 20
𝜙1 > 2 3
3 𝜂=
𝜂 = 2 𝜙1 − 1 𝜙1
𝜙1

DIFFUSION AND REACTION 14

e) Overall reaction rate (Pore diffusion limited)
Variation in reaction rate within a pellet is described by internal effectiveness factor.
−𝑟𝐴 = 𝜂 −𝑟𝐴𝑠
For first order reaction, 𝜂 = 3Τ𝜙1
3
⟹ −𝑟𝐴 = 𝑘 𝐶
𝜙1 1 𝐴𝑠
Using Thiele modulus, 𝜙1 = 𝑅 𝑘1 Τ𝐷𝑒
𝟑 𝟑
−𝒓𝑨 = 𝑫𝒆 𝒌𝟏 𝑪𝑨𝒔 (or) − 𝒓𝑨 = 𝑫𝒆 𝒌′′𝟏 𝝆𝒄 𝑺𝒂 𝑪𝑨𝒔
𝑹 𝑹
How to increase the reaction rate under pore diffusion limited condition?

DIFFUSION AND REACTION 15

Reaction rate for higher reaction orders
Thiele Modulus
𝑘𝑛 𝑅2 𝐶𝐴𝑠 (𝑛−1) 𝑘′′𝑛 𝑆𝑎 𝜌𝑐 𝑅2 𝐶𝐴𝑠 (𝑛−1)
𝜙𝑛 2 = 𝜙𝑛 2 =
𝐷𝑒 𝐷𝑒
Internal Effectiveness
For pore diffusion limited cases, 𝜙𝑛 2 ≫
1ൗ 1ൗ
2 2 3 2 2 3 𝐷𝑒
𝜂= 𝜂= 𝐶𝐴𝑠 (1−𝑛)
𝑛+1 𝜙𝑛 𝑛+1 𝑅 𝑘𝑛
What is the effect of increasing 𝐶𝐴𝑠 on 𝜂 when 𝑛 > 1?
Overall Reaction Rate
−𝑟𝐴 = 𝜂 −𝑟𝐴𝑠 = 𝜂𝑘𝑛 𝐶𝐴𝑠 𝑛
1ൗ
2 2 3 𝐷𝑒 3 2𝐷𝑒 𝑘𝑛
−𝑟𝐴 = 𝐶𝐴𝑠 (1−𝑛) 𝑘𝑛 𝐶𝐴𝑠 𝑛 ⇒ −𝑟𝐴 = 𝐶𝐴𝑠 (𝑛+1)/2
𝑛+1 𝑅 𝑘𝑛 𝑅 𝑛+1

DIFFUSION AND REACTION 16

FLOW, DIFFUSION AND REACTION
◼ External and internal diffusions are of same magnitude.
◼ Molar flow of species from bulk to external surface will be same as net rate of reaction within and on
the pellet.
◼ Overall reaction rate is described in terms of overall effectiveness factor.
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
Ω= 𝐶𝐴𝑠
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑖𝑓 𝑝𝑒𝑙𝑙𝑒𝑡 𝑖𝑛𝑡𝑒𝑟𝑖𝑜𝑟 𝑖𝑠 𝑒𝑥𝑝𝑜𝑠𝑒𝑑 𝑡𝑜 𝐶𝐴𝑏
′ ′′ 𝐶𝐴𝑏 𝐶𝐴
−𝑟𝐴 −𝑟 𝐴 −𝑟 𝐴
Ω= = =
−𝑟𝐴𝑏 −𝑟 ′𝐴𝑏 −𝑟 ′′𝐴𝑏
Overall reaction rate,
−𝑟 ′′𝐴 = Ω −𝑟 ′′𝐴𝑏
First order reaction,
𝜂
𝛺= 𝜌𝑏 = 𝜌𝑐 (1 − ϕ)
𝐷 𝑘′′ 𝜌 𝑆
1+𝜂 𝑒 1 𝑏 𝑎
𝑘𝑐 𝑎𝑐

DIFFUSION AND REACTION 17

HETEROGENEOUS CATALYTIC REACTOR DESIGN
𝒂𝑨 + 𝒃𝑩 ⟶ 𝒄𝑪 + 𝒅𝑫

Reactor Size
Reaction Rate Product
Mole Balance Stoichiometry
Law
Distribution

Batch Reactor
𝑑𝑋𝐴 Pore Diffusion
𝑁𝐴0 = −𝑟′𝐴 𝑊 Stoichiometry
𝑑𝑡 −𝑟′𝐴 = 𝜂 −𝑟 ′𝐴𝑠
𝑑 𝑐 𝑏
PBR 𝛿 = + − −1
(or) 𝑎 𝑎 𝑎
𝑑𝑋𝐴 𝜀𝐴 = 𝑦𝐴0 𝛿
𝐹𝐴0 = −𝑟′𝐴 Flow & Diffusion
𝑑𝑊 𝐶𝐴 1 − 𝑋𝐴 𝑇0 𝑃
Fluidized CSTR −𝑟′𝐴 = Ω −𝑟 ′𝐴𝑏 =
𝑊 𝑋𝐴 𝐶𝐴0 1 + 𝜀𝐴 𝑋𝐴 𝑇 𝑃0
=
𝐹𝐴0 −𝑟′𝐴
DIFFUSION AND REACTION 18
PACKED BED REACTOR DESIGN

𝐹𝐴0 𝐹𝐴𝐿

𝑧=0 𝑧 𝑧 + ∆𝑧 𝑧=𝐿
Catalytic reaction: 𝐴 ⟶ 𝐵
Mole Balance
𝐼𝑛 − 𝑂𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
𝐹𝐴𝑧 ቚ − 𝐹𝐴𝑧 ቚ + 𝑟 ′𝐴 𝜌𝑏 (𝐴𝑐 ∆𝑧) = 0 1 𝑑𝐹𝐴𝑧
𝑧 𝑧+∆𝑧 ÷ 𝐴𝑐 ∆𝑧 & ∆𝑧 → 0 − + 𝑟 ′𝐴 𝜌𝑏 = 0
𝐴𝑐 𝑑𝑧
𝑟 ′𝐴 : Rate of generation of A per unit mass of catalyst
𝜌𝑏 : Bulk density of catalyst 𝜌𝑏 = 𝜌𝑐 (1 − ϕ)
1 𝑑𝐹𝐴𝑧
− + 𝑟𝐴 = 0
𝐴𝑐 : Cross-section area of tube containing catalyst 𝐴𝑐 𝑑𝑧
𝐹𝐴𝑧 : Molar Flow

DIFFUSION AND REACTION 19

Molar Flow 1 𝑑𝐹𝐴𝑧
− + 𝑟𝐴 = 0
𝐹𝐴𝑧 = 𝐴𝑐 𝑊𝐴𝑧 = 𝐴𝑐 (𝐽𝐴𝑧 + 𝐵𝐴𝑧 ) 𝐴𝑐 𝑑𝑧
𝐹𝐴𝑧 = 𝐴𝑐 𝐵𝐴𝑧 𝐽𝐴𝑧 ≪ 𝐵𝐴𝑧 𝐹𝐴𝑧 = 𝐴𝑐 𝐶𝐴𝑏 𝑈
Reaction Kinetics
Flow & Diffusion: −𝑟 ′𝐴 = 𝛺 −𝑟 ′𝐴𝑏
Pore Diffusion: −𝑟𝐴 = 𝜂 −𝑟𝐴𝑏
𝐶𝐴𝑠
𝐶𝐴𝑏 𝐶𝐴 OR 𝐶𝐴𝑏 𝐶𝐴

First order reaction: −𝑟𝐴 = Ω𝑘1 𝐶𝐴𝑏

First order reaction: −𝑟𝐴 = 𝜂𝑘1 𝐶𝐴𝑏
Combine and Solve 3
𝜂= 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1
𝑑𝐶𝐴𝑏 𝜙1 2
𝑈 + 𝜂𝑘1 𝐶𝐴𝑏 = 0 𝜂 independent of 𝐶𝐴𝑏
𝑑𝑧
𝑘1 𝑘′′1 𝑆𝑎 𝜌𝑐
Integrating, 𝜙1 = 𝑅 =𝑅
𝐷𝑒 𝐷𝑒
𝐶𝐴𝑏
𝑑𝐶𝐴𝑏 𝑧
𝑘1 𝜂 𝐶𝐴𝑏 𝑘1 𝜂
න = −න 𝑑𝑧 = 𝐸𝑥𝑝 − 𝑧
𝐶𝐴𝑏0 𝐶𝐴𝑏 0 𝑈
𝐶𝐴𝑏0 𝑈
DIFFUSION AND REACTION 20
Conversion varies along reactor length
𝑘1 𝜂
𝑋𝐴 = 1 − 𝐸𝑥𝑝 − 𝑧
𝑈
Exit Conversion,
𝑘1 𝜂
𝑋 = 1 − 𝐸𝑥𝑝 − 𝐿 𝑘1 = 𝑘′1 𝜌𝑏 = 𝑘′′1 𝜌𝑏 𝑆𝑎
𝑈
Flow & Diffusion Limited
Exit Conversion,
𝑘′′1 𝑆𝑎 𝜌𝑏 Ω
𝑋 = 1 − 𝐸𝑥𝑝 − 𝐿
𝑈
Where, 𝜂
𝛺=
𝐷 𝑘′′ 𝜌 𝑆
1+𝜂 𝑒 1 𝑏 𝑎
𝑘𝑐 𝑎𝑐

3 𝑘1 𝑘′′1 𝑆𝑎 𝜌𝑏
𝜂= 2 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1 ; 𝜙1 = 𝑅 =𝑅
𝜙1 𝐷𝑒 𝐷𝑒

DIFFUSION AND REACTION 21

RATE LIMITING STEP FROM EXPERIMENTAL DATA
External mass transfer limited: −𝑟′𝐴 = 𝑘𝑐 𝑎𝑐 𝐶𝐴
Factors that influence reaction rate
a) Mass Transfer Coefficient
𝐷𝐴𝐵 2Τ3 𝑈 1Τ2
Function of fluid phase and system properties: 𝑘𝑐 ∝
𝜈 1Τ6 𝑑𝑝 1
Τ2

For the same fluid phase,

For the same catalytic bed,
𝑈 1Τ2
𝑘𝑐 ∝ 1Τ2 𝑘𝑐 ∝ 𝑈 1Τ2 𝑇 11Τ12
𝑑𝑝
b) External surface area per volume of bed
1
Function of catalyst particle size: 𝑎𝑐 ∝
𝑑𝑝
𝟏
𝟏Τ 𝟐 −𝒓′𝑨 ∝
−𝒓′𝑨 ∝ 𝑼 −𝒓′𝑨 ∝ 𝑻𝟏𝟏Τ𝟏𝟐 Τ𝟐
𝒅𝒑 𝟑

DIFFUSION AND REACTION 22

Internal mass transfer limited: −𝑟′𝐴 = 𝜂 −𝑟 ′𝐴𝑠

3 2𝐷𝑒 𝑘𝑛
−𝑟′𝐴 = 𝐶𝐴𝑠 (𝑛+1)/2
𝑅 𝑛+1
1
−𝑟′𝐴 ∝ −𝑟′𝐴 varies exponentially with T
𝑑𝑝

Surface reaction limited: −𝑟′𝐴 = 𝑘′𝑛 𝐶𝐴𝑠 𝑛

−𝑟′𝐴 varies exponentially with 𝑇 −𝑟′𝐴 independent of 𝑈 & 𝑑𝑝

Variation of reaction rate with

Limitation
Velocity Particle size Temperature
External Diffusion 𝑈 1Τ2 (𝑑𝑝 )−3Τ2 ≈ 𝐿𝑖𝑛𝑒𝑎𝑟
Internal Diffusion Independent (𝑑𝑝 )−1 Exponential
Surface Reaction Independent Independent Exponential

DIFFUSION AND REACTION 23

EXAMPLE 1
The catalytic reaction 𝐴 → 𝐵 takes place within a fixed bed containing spherical porous catalyst. Figure
shows the overall rates of reaction at a point in the reactor as a function of temperature for various
entering total molar flow rates, 𝐹𝑇0 .
a) Under what conditions is the reaction external diffusion limited?
b) Under what conditions is the reaction surface reaction limited?
c) Under what conditions is the reaction internal diffusion limited?
d) Evaluate 𝜂 when 𝑇 = 367𝐾.
e) If the concentration at the external catalyst surface is 0.01 𝑚𝑜𝑙/𝑑𝑚3 , calculate the concentration at
𝑟 = 𝑅/2 inside the porous catalyst at 367 𝐾. (Assume a first-order reaction).

DIFFUSION AND REACTION 24

 Overall reaction rate as a function of temperature and molar feed rate

DIFFUSION AND REACTION 25

a) External diffusion limited
Reaction rate increases linearly with temperature.

DIFFUSION AND REACTION 26

b) Surface reaction limited
Reaction rate increases exponentially with temperature and independent of molar flow rate.

DIFFUSION AND REACTION 27

c) Pore diffusion limited
Reaction rate increases exponentially with temperature (but not as strong as surface reaction limited)
and independent of molar flow rate.

DIFFUSION AND REACTION 28

d) Internal effectiveness factor at 367 𝐾
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 −𝑟 ′𝐴
𝜂= =
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑖𝑓 𝑝𝑒𝑙𝑙𝑒𝑡 𝑖𝑛𝑡𝑒𝑟𝑖𝑜𝑟 𝑖𝑠 𝑒𝑥𝑝𝑜𝑠𝑒𝑑 𝑡𝑜 𝐶𝐴𝑠 −𝑟 ′𝐴𝑠

DIFFUSION AND REACTION 29

e) Concentration at 𝑟 = 𝑅Τ2, 367 𝐾
Pore diffusion limited
Reaction rate increases exponentially with temperature (but not as strong as surface reaction limited)
and independent of molar flow rate.

DIFFUSION AND REACTION 30

Concentration at 𝑟 = 𝑅Τ2, 367 𝐾
Pore diffusion limited: 𝐹𝑇0 = 1000 𝑔 𝑚𝑜𝑙Τℎ𝑟 & 5000 𝑔 𝑚𝑜𝑙Τℎ𝑟, 𝑇 > 367 𝐾
For first order reaction, concentration profile within pellet,
1 𝑠𝑖𝑛ℎ𝜙1 𝜆
𝐶𝐴 = 𝐶𝐴𝑠
𝜆 𝑠𝑖𝑛ℎ𝜙1
𝜙1 : Thiele modulus (first order reaction)
𝜆: Dimensionless radial distance
Using,
Using,
3
𝜂 = 2 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1 = 0.86 𝑟 𝑅Τ2
𝜙1 𝜆= =
𝑅 𝑅
𝜙1 = 1.6
𝜆 = 1Τ2
Combining,
sinh 1.6/2
𝐶𝐴 ቚ = (0.01)(2)
𝑟=𝑅 Τ2 sinh(1.6)
𝐶𝐴 ቚ = 0.0075 𝑚𝑜𝑙 Τ𝑑𝑚3
𝑟=𝑅 Τ2

DIFFUSION AND REACTION 31

SUMMARY
◼ Pore Diffusion: Defined in terms of effective diffusion coefficient and concentration gradient.
𝑑𝐶𝐴
𝑊𝐴𝑟 = −𝐷𝑒
𝑑𝑟
◼ Pore Diffusion and Reaction
❑ Internal effectiveness factor: Describes the variation of reaction rate within the pellet.
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
𝜂=
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑖𝑓 𝑝𝑒𝑙𝑙𝑒𝑡 𝑖𝑛𝑡𝑒𝑟𝑖𝑜𝑟 𝑖𝑠 𝑒𝑥𝑝𝑜𝑠𝑒𝑑 𝑡𝑜 𝐶𝐴𝑠
1ൗ
3 2 23
𝜂= 𝜙1 𝑐𝑜𝑡ℎ𝜙1 − 1 𝜂=
𝜙1 2 𝑛+1 𝜙𝑛
❑ Thiele modulus: Measure of ratio of surface reaction rate to diffusion rate through the catalyst
pellet.
2 𝑘𝑛 𝑅2 𝐶𝐴𝑠 (𝑛−1)
𝜙𝑛 =
𝐷𝑒

DIFFUSION AND REACTION 32

SUMMARY
◼ Flow, Diffusion and Reaction
❑ Molar flow of species from bulk to external surface will be same as net rate of reaction within and
on the pellet.
❑ Overall effectiveness factor: Used when external and internal diffusion are of same magnitude.
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
Ω=
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑖𝑓 𝑝𝑒𝑙𝑙𝑒𝑡 𝑖𝑛𝑡𝑒𝑟𝑖𝑜𝑟 𝑖𝑠 𝑒𝑥𝑝𝑜𝑠𝑒𝑑 𝑡𝑜 𝐶𝐴𝑏
𝜂
𝛺=
𝐷 𝑘′′ 𝜌 𝑆
1+𝜂 𝑒 1 𝑏 𝑎
𝑘𝑐 𝑎𝑐
◼ PBR design for mass transfer limited reaction
❑ Reaction rate and species concentration/conversion varies along the reactor length.
𝐶𝐴𝑏 𝑘′′1 𝑆𝑎 𝜌𝑏 Ω 𝑘′′1 𝑆𝑎 𝜌𝑏 Ω
= 𝐸𝑥𝑝 − 𝑧 𝑋𝐴 = 1 − 𝐸𝑥𝑝 − 𝑧
𝐶𝐴𝑏0 𝑈 𝑈

DIFFUSION AND REACTION 33

SUMMARY

◼ PBR design for internal mass transfer limited reaction

Reaction rate and species concentration/conversion varies along the reactor length.
For first order reaction, −𝑟𝐴 = 𝜂𝑘1 𝐶𝐴𝑏

Concentration Conversion
𝐶𝐴𝑏 𝑘1 𝜂 𝑘1 𝜂
= 𝐸𝑥𝑝 − 𝑧 𝑋𝐴 = 1 − 𝐸𝑥𝑝 − 𝑧
𝐶𝐴𝑏0 𝑈 𝑈

◼ Rate limiting step from experimental data

Variation of reaction rate with
Limitation
Velocity Particle size Temperature
External Diffusion 𝑈 1Τ2 (𝑑𝑝 )−3Τ2 ≈ 𝐿𝑖𝑛𝑒𝑎𝑟
Internal Diffusion Independent (𝑑𝑝 )−1 Exponential
Surface Reaction Independent Independent Exponential
DIFFUSION AND REACTION 34