CL208/ CL324

CHEMICAL REACTION
ENGINEERING

Week 13

1
Typical Heterogeneous Catalyst

Active Site

ACTIVE SITES
CATALYST PELLET
REACTOR CATALYST PORES - MOLECULAR
- 0.1 – 10 mm
- metres - 0.5 – 100 nm SCALE (Angstrom)
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Steps in heterogeneous Catalysis

A→B

3
Physical & chemical processes in a reactor containing catalyst particles
𝑨 ( 𝒈) → 𝑹( 𝒈)
𝐶 𝐴𝑏
1. 𝐹𝑙𝑢𝑥 =𝑘𝑔 ( 𝐶 𝐴 , 𝑏 −𝐶 𝐴 ,𝑠 )
Mass transfer of A from bulk gas phase to catalyst
pellet surface.
𝑑 𝐶𝐴
𝐹𝑙𝑢𝑥 =− 𝐷 x
2. Diffusion of A through pores to catalyst surface 𝑑𝑥
Langmuir
3. Adsorption of A on catalytic site 𝐴3 5 Hinshelwood model
4 𝑅
𝑘 𝐶𝐴
𝐴𝑅 𝑅𝑎𝑡𝑒=
4. Catalytic conversion of A to R on catalyst surface 1+ 𝐾 3 𝐶 𝐴 + 𝐾 5 𝐶

5. Desorption of R from catalytic site Surface kinetics/ reaction n

Power law

𝑑𝐶𝑅
6. 𝐹𝑙𝑢𝑥 = 𝐷
Diffusion of R through pores back to catalyst pellet
𝑑𝑥
surface

7. Mass transfer of R from catalyst pellet surface to bulk 𝐹𝑙𝑢𝑥

gas =𝑘𝑔 ( 𝐶 𝑅 , 𝑠 −𝐶 𝑅 , 𝑏 ) 𝐶 𝑅𝑠
phase

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Intraparticle Mass Transfer - Diffusion
Find concentration profile of A in catalyst particle

Rate of consumption of A by reaction per unit catalyst 𝑘 𝐶 = 𝜌 𝑆 𝑘′ ′ 𝐶𝐴

𝐴 𝑐 𝑎 𝑟
volume =

Concentration of A inside catalyst pores changes as a function of𝐶

r: 𝐴 = 𝑓 (𝑟 )

To find CA = f(r), consider a differential shell of thickness ∆r at radial distance of r

𝐼𝑛− 𝑂𝑢𝑡 − 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛= 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 At steady state

Mole balance of A over the shell:

=0 ⟹=0

Boundary conditions: is finite

Assuming external mass transfer is very fast

5
Intra-particle concentration gradients
=0 Boundary conditions =
𝑑𝐶𝐴
2 . 𝑟=0 , =0
𝑟 𝐶𝐴 𝑑𝑟
Non-dimensionalize: 𝜌= ; 𝜃=
𝑅 𝐶 𝐴𝑏

=0 Boundary conditions
𝑑𝜃
2 . 𝜌=0 , =0 𝑜𝑟 , 𝜃 is finite

√
𝑑𝜌
𝑘𝑠
𝐷𝑒𝑓𝑖𝑛𝑒 𝜙 =
2
❑
𝑘
𝐷𝑒 (
⟹
𝑅
2
𝜙 ❑= 𝑅 ) 𝐷𝑒
Thiele modulus

2nd order non-linear ODE – use transformation

𝐶 1 sinh ⁡( 𝜙𝜌 ) +𝐶 2 cos h ⁡( 𝜙𝜌 ) From BC 2, 𝐶 2 =0

⟹ 𝜃=
𝜌 𝜌 1
From BC 1, 𝐶 1 =
sinh 𝜙
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Intra-particle concentration gradients

√ 𝑘
( 𝜙 ¿𝑟 / 𝑅)
sinh ( 𝜙 𝜌 ) 𝐶 𝐴 =𝐶 𝐴 ,𝑏 sinh ¿
𝜃= ⟹ 𝑟
( ) sinh 𝜙 𝑤h𝑒𝑟𝑒 𝜙❑=𝑅
𝜌 sinh 𝜙 𝑅 𝐷𝑒

For high , interior parts of the

catalyst is starved of A

2 𝑎 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
𝜙 =
𝑎 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒

Low Thiele modulus → CA inside pellet is close to CAs

High Thiele modulus → CA drops with radial distance

→ The entire surface area/ volume of the catalyst is not utilized i.e. catalyst is not 100% effective
7
Intra-particle effectiveness factor

Intra-phase Effectiveness factor:

Actual rate of consumption of A in the catalyst pellet =

Rate of consumption of A if there were no mass transfer effects =

Reaction limited
⟹ 𝜂=
3
( 1
−
1
𝜙❑ 𝑡𝑎𝑛h 𝜙❑ 𝜙❑ )
𝑘
√
For spherical particle
𝑤h 𝑒𝑟𝑒 𝜙=𝑅
𝐷𝑒 Diffusion
limited

8
Diffusion in porous solid
Diffusion of A (gas) in straight cylindrical pore
𝑑𝐶𝐴
𝐷𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑒 𝑓𝑙𝑢𝑥 𝑜𝑓 𝐴 : 𝑗 𝐴=− 𝐷
𝑑𝑥

• Molecular Diffusion
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦 𝐷 𝑀 • Determined experimentally for binary gas mixtures

( )
3
−3 2 1 1
• Can be estimated from kinetic theory of gases 10 𝑇 +
𝑀1 𝑀2
assuming rigid spheres or from Chapman-Enskog 𝐷 𝑀 =1.86 . 2
Theory 𝑃 𝜎 12 Ω

• Knudsen Diffusion D values at STP

When pore diameter < mean free path of gas molecule. ~10-1 cm2/s
example, mean free path of O2 at room temp,
1 atm ~ 50 nm
~10-2 to 10-3
𝐾𝑛𝑢𝑑𝑠𝑒𝑛 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦 𝐷 𝐾 cm2/s

𝐷𝐾 =
√
𝑑 𝑝𝑜𝑟𝑒 8 𝑅𝑇
3 𝜋 𝑀 𝑑𝑝 𝑜𝑟𝑒 =𝑝𝑜𝑟𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟
Knudsen diffusion important for gas diffusion
in mesoporous solids

9
Diffusion in porous solid
Diffusion of A (gas) in pores Additional factors:

• Pores are not straight cylinders – they are tortuous

• The available surface area for diffusion in the pellet is

only the void portion
Define a new parameter Effective Diffusivity De
that characterizes diffusion through the entire
particle as a whole.

𝜀𝑝 𝐷
𝐷 𝑒=𝑒𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦= where , 𝜀𝑝 = particle porosity ; τ = tortuosity factor
𝜏

2 2
𝐷𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑡h𝑟𝑜𝑢𝑔h 𝑠𝑝h𝑒𝑟𝑖𝑐𝑎𝑙 𝑝𝑒𝑙𝑙𝑒𝑡=4 𝜋 𝑅 𝐽 𝐴=4 𝜋 𝑅 − 𝐷𝑒 (
𝑑𝐶𝐴
𝑑𝑟 )
10
Analysis of Influence of Mass Transport in Catalyst Pores

QUALITATIVE CONSIDERATIONS:
if catalyst pore diameter is small, transport of reactants & products
may be prevented → shape-selective catalysis

if catalyst pore diameter is large, resistance to transport in the

pores may be negligible

in intermediate case, transport restriction may be significant, and

both rates of diffusion and reaction will affect the overall
conversion rate

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