UNIT 10: CATALYST DEACTIVATION

Recommended Reading: HSF Chapter 10.7

LEARNING OBJECTIVES

◼ Understand catalyst decay kinetics.

◼ Design catalytic reactors with catalyst decay.

CATALYST DEACTIVATION 2
OUTLINE

◼ Catalyst Deactivation
◼ Catalyst deactivation kinetics
◼ Reactor Design with Catalyst Decay
◼ Reactor systems to overcome Catalyst Decay

CATALYST DEACTIVATION 3
CATALYST DEACTIVATION

Decline in catalyst activity (𝐶𝑡 ) with time

(Slow/Moderate/Fast)
Causes for catalyst decay
◼ Aging: Change in the crystal structure of catalyst
◼ Poisoning: Irreversible deposition of species on the active site
◼ Fouling/Coking: Deposition of carbonaceous material on the surface
Effect of catalyst decay
◼ Affects reaction kinetics
◼ Reaction Pathway
◼ Decreases the lifetime of catalyst

CATALYST DEACTIVATION 4
CATALYST DEACTIVATION KINETICS
−𝑟 ′𝐴 (𝑡)
Activity of the catalyst: 𝑎 𝑡 =
−𝑟 ′𝐴 (𝑡 = 0)
Rate of catalyst decay,
𝑑𝑎
𝑟𝑑 = − = 𝑝(𝑎)𝑘𝑑 (𝑇)ℎ(𝐶𝑖 )
𝑑𝑡
Species Concentration
Specific decay constant: Temperature Dependent
Functionality of activity
Catalytic reactor design: −𝒓′ 𝑨 = 𝒂(𝒕) −𝒓′ 𝑨 (𝒕 = 𝟎)
−𝑟 ′𝐴 = 𝑎 𝑡 𝑘 𝑇 𝑓𝑛(𝐶𝑖 )
Species Concentration
Specific reaction rate: Temperature Dependent
Catalytic activity: Time Dependent

SEPARABLE KINETICS
CATALYST DEACTIVATION 5
Deactivation by Sintering
Loss of catalytic activity due to prolonged exposure to high temperature.
What happens to catalyst surface?
◼ Crystal agglomeration and growth of metals deposited on the support.
◼ Narrowing or closing of pores.
◼ Surface recrystallization.
◼ Formation or elimination of surface defects.

𝑡=0 𝑡 𝑤𝑎𝑠𝑡𝑒𝑑 𝑠𝑢𝑟𝑓𝑎𝑐𝑒

𝑑𝑎 2 1
Decay kinetics: 𝑟𝑑 = − = 𝑘𝑑 𝑎 ⟹ 𝑎 𝑡 =
𝑑𝑡 1 + 𝑘𝑑 𝑡
𝐸𝑑 1 1
𝑘𝑑 = 𝑘𝑑 𝑇0 𝐸𝑥𝑝 − Reduced by keeping 𝑇 < 0.4𝑇𝑚
𝑅 𝑇0 𝑇
CATALYST DEACTIVATION 6
Deactivation by Coking

Loss of activity due to deposit of carbonaceous material

𝑡=0 𝑡

Amount of coke on surface: 𝐶𝐶 = 𝐴𝑡 𝑛

Activity: 1 1
𝑎= 𝑜𝑟 𝑎=
1 + 𝑘𝐶𝑘 𝐶𝐶 𝑝 1 + 𝑘′𝑡 𝑚
Reduce Coking: Elevated pressure and hydrogen rich-streams.
Catalyst Regeneration: Burning off Carbon

CATALYST DEACTIVATION 7
Deactivation by Poisoning

Loss of activity due to irreversible chemisorption of molecules to active sites

P B
B A P P A P P P P P

𝑡=0 𝑡1 𝑡2

Poison: Reactants/Products/ Impurity

𝑑𝑎
Decay Kinetics: 𝑟𝑑 = − = 𝑘𝑑 𝑎 𝑡 𝐶𝑃
𝑑𝑡

How to restore poisoned catalyst?

CATALYST DEACTIVATION 8
Decay Rate Law
𝑑𝑎
𝑟𝑑 = − = 𝑝(𝑎)𝑘𝑑 (𝑇)ℎ(𝐶𝑖 )
𝑑𝑡
Decay Reaction
Functional Form Differential Form Integral Form
Order

𝑑𝑎 𝑎 = 1 − 𝛽0 𝑡
Linear 0 − = 𝛽0
𝑑𝑡

𝑑𝑎 𝑎 = 𝑒 −𝛽1𝑡
Exponential 1 − = 𝛽1 𝑎
𝑑𝑡

𝑑𝑎 1
Hyperbolic 2 − = 𝛽2 𝑎2 = 1 + 𝛽2 𝑡
𝑑𝑡 𝑎

CATALYST DEACTIVATION 9
REACTOR DESIGN WITH CATALYST DECAY
𝒂𝑨 + 𝒃𝑩 ⟶ 𝒄𝑪 + 𝒅𝑫

Reaction Rate Law Reactor Size

Mole Balance Stoichiometry Product
Decay Rate Law Distribution

Batch Reactor
𝑑𝑋𝐴 Stoichiometry
𝑁𝐴0 = −𝑟′𝐴 𝑊
𝑑𝑡 𝑑 𝑐 𝑏
PBR −𝑟 ′𝐴 = 𝑎 𝑡 −𝑟 ′𝐴 (𝑡 = 0) 𝛿 = + − −1
𝑎 𝑎 𝑎
𝑑𝑋𝐴 𝜀𝐴 = 𝑦𝐴0 𝛿
𝐹𝐴0 = −𝑟′𝐴
𝑑𝑊 𝑑𝑎
𝑟𝑑 = − = 𝑝(𝑎)𝑘𝑑 (𝑇)ℎ(𝐶𝑖 ) 𝐶𝐴 1 − 𝑋𝐴 𝑇0 𝑃
Fluidized CSTR 𝑑𝑡 =
𝑊 𝑋𝐴 𝐶𝐴0 1 + 𝜀𝐴 𝑋𝐴 𝑇 𝑃0
=
𝐹𝐴0 −𝑟′𝐴
CATALYST DEACTIVATION 10
EXAMPLE 1

An isomerization reaction is carried out in a packed bed reactor at 490 𝐾 (pure A at 2 𝑎𝑡𝑚, 𝐹𝐴0 =
0.5 𝑘𝑚𝑜𝑙/ℎ𝑟 and 𝑊 = 100 𝑘𝑔 ). The catalyst deactivates following zero order decay.
a) Plot catalyst activity as a function of time. When should the catalyst be regenerated?
b) Plot exit conversion as a function of time.
Additional Data:
−𝑟 ′𝐴 = 0.2𝐶𝐴 2 𝑚𝑜𝑙 𝐴Τ𝑘𝑔 𝑐𝑎𝑡 − ℎ𝑟

𝑑𝑎
− = 0.05 ℎ𝑟 −1
𝑑𝑡

CATALYST DEACTIVATION 11
SOLUTION
a) Catalyst activity
𝑑𝑎
Decay kinetics: 𝑟𝑑 = − = 𝑝(𝑎)𝑘𝑑 (𝑇)ℎ(𝐶𝑖 )
𝑑𝑡
Decay Rate: Zero order decay
𝑝 𝑎 = 𝑎0 ℎ 𝐶𝑖 = 1
𝑑𝑎
⟹ 𝑟𝑑 = − = 𝑘𝑑
𝑑𝑡
𝑑𝑎
− = 0.05
𝑑𝑡
Integrating,
𝑎 𝑡
න −𝑑𝑎 = න (0.05)𝑑𝑡
1 0
𝒂 𝒕 = 𝟏 − 𝟎. 𝟎𝟓𝒕
Catalytic activity decreases linearly with time.
Regeneration Time: 𝒕 = 𝟐𝟎 𝒉𝒓
CATALYST DEACTIVATION 12
b) Exit Conversion
Mole Balance
𝑑𝑋𝐴
𝐹𝐴0 = −𝑟′𝐴
𝑑𝑊
100 𝑋𝐴
𝑑𝑋𝐴
න 𝑑𝑊 = 𝐹𝐴0 න
0 0 −𝑟′𝐴
Reaction Kinetics
−𝑟 ′𝐴 = 𝑎 𝑡 −𝑟 ′𝐴 (𝑡 = 0)
−𝑟 ′𝐴 = 𝑎 𝑡 0.2𝐶𝐴 2
Decay Rate Law
𝑎 𝑡 = 1 − 0.05𝑡
Stoichiometry
𝐶𝐴 1 − 𝑋𝐴 𝑃𝐴0 2 𝑎𝑡𝑚
= 𝐶𝐴0 = = 3 = 50 𝑚𝑜𝑙 Τ𝑚3
𝐶𝐴0 1 + 𝜀𝐴 𝑋𝐴 𝑅𝑇 𝑚 . 𝑎𝑡𝑚
82.06 × 10−6 (490 𝐾)
𝑚𝑜𝑙. 𝐾
𝐶𝐴 = 50(1 − 𝑋𝐴 )

CATALYST DEACTIVATION 13
Combine and Solve
100 𝑋𝐴
𝑑𝑋𝐴
න 𝑑𝑊 = 𝐹𝐴0 න
0 0 −𝑟′𝐴
𝑋𝐴
0.5 × 103 𝑑𝑋𝐴
100 = න
(1 − 0.05𝑡) × 0.2 × 50 0 (1 − 𝑋𝐴 ) 2
2

𝟏𝟎𝟎(𝟏 − 𝟎. 𝟎𝟓𝒕)
𝑿𝑨 =
𝟏 + 𝟏𝟎𝟎(𝟏 − 𝟎. 𝟎𝟓𝒕)

When is it appropriate to regenerate

the catalyst?

CATALYST DEACTIVATION 14
OVERCOME CATALYST DECAY

Temperature-Time Trajectories Straight-Through

Moving Bed Reactor
Transport Reactor
Change in T to compensate Flow of catalyst relative to reactants to compensate
decrease in catalytic activity. decrease in catalytic activity.
CATALYST DEACTIVATION 15
Moving Bed Reactor

Reactants: Moves through the reactor (𝑣0 )

relative to catalyst flow.
Catalyst: Moves through the reactor as a
compact bed (𝑈𝑠 ) and loses its activity (𝑟𝑑 ).
Catalyst Regeneration: Kiln
Steady state: Feed rate of catalyst and
reactants does not vary with time.

𝒂 = 𝒈 𝒕 𝒐𝒓 𝒂 = 𝒈(𝒛)
𝑿 = 𝒇(𝒛)

CATALYST DEACTIVATION 16
Reactor Design
Mole Balance on A
𝐹𝐴 ቚ − 𝐹𝐴 ቚ + 𝑟 ′𝐴 𝑊 = 0
𝑊 𝑊+∆𝑊
𝑑𝑋𝐴
𝐹𝐴0 = −𝑟′𝐴
𝑑𝑊
Reaction Kinetics
−𝑟 ′𝐴 = 𝑎 𝑡 −𝑟 ′𝐴 (𝑡 = 0)
−𝑟 ′𝐴 = 𝑎 𝑡 𝑘𝑓𝑛(𝐶𝑖 )
Decay Rate Law
𝑿 = 𝒇(𝑾)
𝑑𝑎
𝑟𝑑 = − = 𝑘𝑑 𝑎𝑛
𝑑𝑡
Catalyst Contact Time,
𝑊 𝑑𝑊
𝑡= ⟹ 𝑑𝑡 =
𝑈𝑠 𝑈𝑠
𝑑𝑎 𝑘𝑑 𝑛
− = 𝑎
𝑑𝑊 𝑈𝑠
CATALYST DEACTIVATION 17
EXAMPLE 2

The elementary isothermal gas-phase reaction is carried out in a moving bed reactor.
𝐴+𝐵 ⟶𝐶+𝐷 𝑘 = 1.0 𝑑𝑚6 Τ(𝑚𝑜𝑙. 𝑘𝑔 𝑐𝑎𝑡. 𝑠)
The reactor contains 2 𝑘𝑔 of catalyst. The feed is stoichiometric in A and B and the volumetric flow rate
is 1 𝑑𝑚3 Τ𝑠. The entering concentration of A is 0.2 𝑚𝑜𝑙 Τ𝑑𝑚3 . The catalyst decay is zero order with
𝑘𝑑 = 0.2 𝑠 −1 . What is the conversion if the catalyst feed rate is 0.5 𝑘𝑔Τ𝑠?

CATALYST DEACTIVATION 18
SOLUTION
Mole Balance
𝑑𝑋𝐴
𝐹𝐴0 = −𝑟′𝐴
𝑑𝑊
Reaction Kinetics
−𝑟 ′𝐴 = 𝑎 𝑡 −𝑟 ′𝐴 (𝑡 = 0)
−𝑟 ′𝐴 = 𝑎 𝑡 𝑘𝐶𝐴 2
Decay Rate Law
𝑑𝑎
Zero order decay: 𝑟𝑑 = − = 𝑘𝑑
𝑑𝑡
Catalyst Contact Time: 𝑑𝑡 = 𝑑𝑊 Τ𝑈𝑠
Combining, 𝑑𝑎 𝑘𝑑
− =
𝑑𝑊 𝑈𝑠
Integrating,
𝑘𝑑 𝑊
𝑎 =1−
𝑈𝑠
𝑎 = 1 − 0.4𝑊 Catalytic activity decreases linearly along the catalyst bed
CATALYST DEACTIVATION 19
Stoichiometry
𝐶𝐴 1 − 𝑋𝐴
=
𝐶𝐴0 1 + 𝜀𝐴 𝑋𝐴
𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 ) 𝜀𝐴 = 0
Combine and Solve
𝑑𝑋𝐴 𝑘𝑑 𝑊
𝐹𝐴0 = 1− 𝑘𝐶𝐴0 2 1 − 𝑋𝐴 2
𝑑𝑊 𝑈𝑠
Separating and Integrating,
𝑋𝐴
𝑑𝑋𝐴 𝑘𝐶𝐴0 𝑊 𝑘𝑑 𝑊
න 2
= න 1− 𝑑𝑊
0 1 − 𝑋𝐴 𝑣0 0 𝑈𝑠
𝑋𝐴 𝑘𝐶𝐴0 𝑘𝑑 𝑊 2
= 𝑊−
1 − 𝑋𝐴 𝑣0 2𝑈𝑠 𝐶𝐴0 = 0.2 𝑚𝑜𝑙 Τ𝑑𝑚3
Using the parameters, 𝑣0 = 1 𝑑𝑚3 Τ𝑠
𝑘 = 1.0 𝑑𝑚6 Τ(𝑚𝑜𝑙. 𝑘𝑔 𝑐𝑎𝑡. 𝑠)
𝑿𝑨 = 𝟏𝟗% 𝑘𝑑 = 0.2 𝑠 −1
𝑈𝑠 = 0.5 𝑘𝑔Τ𝑠

CATALYST DEACTIVATION 20
SUMMARY
◼ Catalyst deactivation
❑ Decline in catalyst activity due to loss of active surface area.
❑ Causes: Aging, Fouling, Poisoning
❑ Effects: Affects reaction kinetics, pathway, catalyst lifetime
◼ Separation Kinetics: Describes catalyst decay and reaction kinetics independently.
−𝑟 ′𝐴
𝑎 𝑡 =
−𝑟 ′𝐴 (𝑡 = 0)
𝑑𝑎
𝑟𝑑 = − = 𝑝(𝑎)𝑘𝑑 (𝑇)ℎ(𝐶𝑖 )
𝑑𝑡
𝑎: Catalyst activity
𝑝(𝑎): Functionality of activity (zero/first/second order)
𝑘𝑑 (𝑇): Catalyst decay constant (Arrhenius Temperature Dependence)
ℎ(𝐶𝑖 ): Functionality of species concentration
CATALYST DEACTIVATION 21
SUMMARY
Reactor design with catalyst decay
𝑎𝐴 + 𝑏𝐵 ⟶ 𝑐𝐶 + 𝑑𝐷

Reaction Rate Law Reactor Size

Mole Balance Stoichiometry Product
Decay Rate Law Distribution

Batch Reactor
𝑑𝑋𝐴 Stoichiometry
𝑁𝐴0 = −𝑟′𝐴 𝑊
𝑑𝑡 𝑑 𝑐 𝑏
PBR −𝑟 ′𝐴 = 𝑎 𝑡 −𝑟 ′𝐴 (𝑡 = 0) 𝛿 = + − −1
𝑎 𝑎 𝑎
𝑑𝑋𝐴 𝜀𝐴 = 𝑦𝐴0 𝛿
𝐹𝐴0 = −𝑟′𝐴
𝑑𝑊 𝑑𝑎
𝑟𝑑 = − = 𝑝(𝑎)𝑘𝑑 (𝑇)ℎ(𝐶𝑖 ) 𝐶𝐴 1 − 𝑋𝐴 𝑇0 𝑃
Fluidized CSTR 𝑑𝑡 =
𝑊 𝑋𝐴 𝐶𝐴0 1 + 𝜀𝐴 𝑋𝐴 𝑇 𝑃0
=
𝐹𝐴0 −𝑟′𝐴
CATALYST DEACTIVATION 22
SUMMARY
◼ Overcome catalyst decay
❑ Temperature Time Trajectories: Vary the feed temperature such that the reaction rate is
unaffected due to catalyst decay.
❑ Moving Bed Reactor/Straight-Through Transport: Flow of catalyst relative to reactants to
compensate catalyst decay.

CATALYST DEACTIVATION 23
Rate law for Heterogeneous Catalytic Reactions
➢ What is the general form of rate law for surface reaction limited
conditions?
𝐾𝑖𝑛𝑒𝑡𝑖𝑐𝑠 𝑇𝑒𝑟𝑚 𝐷𝑟𝑖𝑣𝑖𝑛𝑔 𝐹𝑜𝑟𝑐𝑒
𝑟𝑎𝑡𝑒 =
(𝐴𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝐺𝑟𝑜𝑢𝑝)𝑛
➢ What are components in the kinetics term?
Reaction rate constant, equilibrium constant and concentration of active
sites.
𝐶6 𝐻5 𝐶𝐻 𝐶𝐻3 2 ⟶ 𝐶6 𝐻6 + 𝐶3 𝐻8
𝐶 ⟶𝐵+𝑃
𝑘 𝑃𝐶 − 𝑃𝐵 𝑃𝑃 Τ𝐾𝑃
′
−𝑟 𝐶 = 𝑘 = 𝐶𝑡 𝑘𝑆 𝐾𝐶
1 + 𝐾𝐵 𝑃𝐵 + 𝐾𝐶 𝑃𝐶
Will 𝐶𝑡 remain as a constant?
Under what circumstances it will change?
How to account for the change in the rate law?
CATALYST DEACTIVATION 24