CL208/ CL324

CHEMICAL REACTION
ENGINEERING

Week 12

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)
2
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

4
External Mass Transfer in Heterogeneous Catalysts

𝐼𝑛− 𝑂𝑢𝑡 − 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛= 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛At steady state

Mass balance of A
over the catalyst
particle:
𝐴𝑝 𝑘𝑐 (𝐶 𝐴𝑏 −𝐶 ¿ ¿ 𝐴 𝑠)= 𝐴𝑝 𝑘𝑟 𝐶 𝐴𝑠 ¿

𝐶 𝐴𝑏
𝐶 𝐴𝑠 =
⟹ ( 1+
𝑘𝑟
)
𝑘𝑐

𝐶 𝐴𝑏
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒=𝑘𝑟 𝐶 𝐴𝑠 =
( 1
+
1
𝑘𝑠 𝑘𝑐 )
Resistances of physical and chemical rate processes in series

5
External Mass Transfer in Heterogeneous Catalysts
𝐶 𝐴𝑏
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 , 𝑟 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 =𝑘𝑟 𝐶 𝐴𝑠=
( 1
+
1
𝑘𝑟 𝑘𝑐 )
𝑘𝑐 ≫ 𝑘𝑟
𝐶 𝐴𝑏 𝐶 𝐴𝑠
𝐶 𝐴𝑏
When 1 . 𝑘 𝑟 ≪ 𝑘 𝑐 , 𝑟 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 = =𝑘 𝑟 𝐶 𝐴 𝑏
Reaction controlled
( 1
𝑘𝑟
+
1
𝑘𝑐 )
𝐶 𝐴𝑏
𝐶 𝐴𝑠 =0
2 . 𝑘𝑟 ≫ 𝑘 𝑐 , 𝑟 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 = 𝑐 𝐶transfer
=𝑘Mass 𝐴𝑏 controlled 𝑘𝑐 ≪ 𝑘𝑟
( 1
𝑘𝑟
+
1
𝑘𝑐 )

𝑅𝑎𝑡𝑒=𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚

𝑀 . 𝑇 . 𝑅𝑎𝑡𝑒=𝑘𝑐 ∗(𝐶 𝐴𝑏 −𝐶 𝐴𝑠)
External Mass Transfer in Heterogeneous Catalysts
How do you calculate ?
Correlations:
For flow around a spherical particle:

How these processes manifest in experimental kinetic rate measurements

Arrhenius plot
ln robserved

M.T.
controlled

1/T