Reactor- en Procestechnologie

Reactor and Process Technology

Catalyst deactivation
L6

Prof. dr. ir. Johan De Greef

Prof. dr. ing. Sam Crauwels

2 7/11/2023 FIIW / FET

Catalyst deactivation Example: SCR

Type Name Cause/Explanation Remediation
Coverage of a catalytic surface by (1) Physical or chemical
FOULING deposition of undesired particles/droplets from cleaning (dis-/semi-/ fully
(COKING) the fluid or (2) chemical growth of undesired continuous)
product layer on catalytic sites
Reduced access to catalytic sites by (1) Replacement
Physical SINTERING deformation of the support material, (2) (discontinuous)
(AGEING) agglomeration of catalyst particles or catalytic
sites (on a surface)
Catalyst management strategy!
Loss in weight of catalytically active material Addition of fresh catalyst
ATTRITION
ABRASION
due to friction by a dust-loaden fluid flow or particles (continuous) regeneration >?< replacement
inter-particle collisions
Total or partial elimination of catalytic sites by Replacement (in some new cata >?< regenerated cata
Chemical POISONING formation of chemical bonds (remark: also cases regeneration also
intentionally applied to change selectivity !!) possible) (discontinuous) Selective Catalytic Reduction

3 7/11/2023 FIIW / FET 4 7/11/2023 https://www.powermag.com/environmentally-sound-handling-of-deactivated-scr-catalyst/ FIIW / FET

 Costs not considered here:
Example: low-T SCR – poisoning by ammonium salts Example: SCR – financial production downtime, installation works,
transport, disposal, fuels/chemicals for
shutdown and startup, administration, etc
Coal plant of 500 MWth
1.40 m³ cata per MWth
annual escalation: 3%

Liu, C.; Wang, H.; Zhang, Z.; Liu, Q. The Latest Research Progress of NH3-SCR in the
5 7/11/2023 SO2 Resistance of the Catalyst in Low Temperatures for Selective Catalytic Reduction of FIIW / FET 6 7/11/2023 https://www.powermag.com/environmentally-sound-handling-of-deactivated-scr-catalyst/ FIIW / FET
NOx. Catalysts 2020, 10, 1034. https://doi.org/10.3390/catal10091034

Examples: other Common mechanisms of catalyst deactivation

• Poisoning • Parallel Poisoning by a reagent
• Nox converters for engines fuelled by leaded gasoline (in the old days):
• Poisoning due to formation of PbO/PbCl2
• Electrochemical fuel cells: • Series Poisoning by a product

• Poisoning due to sulfur-based compounds and CO

• Ziegler-Natta catalysts for olefine polymerization Poisoning by some other
• ZN catalyst = transition metal (Ti, Zr, Hf) + organo-aluminum compound (Al(Et)3) • Side-by-side substance in the feed
• Poisoning due to … H2O and O2

• Enzyme inhibition: biochemical analogue of catalyst poisoning • Independent of concentration E.g. attrition

• Hemoglobin
• Poisoning/Inhibition due to CO occupying the active sites instead of O2

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Catalyst activity and deactivation rate Common kinetics of catalyst deactivation
remaining surface concentration of catalytic sites
=
initial surface concentration of catalytic sites

‘a’ is considered a non-dimensional

concentration that follows the standard
type kinetics of a reaction (mCi+da → P)
with an apparent Arrhenius constant kd
a

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Catalyst with pore diffusion resistance Catalyst with pore diffusion resistance

Paradox effect: The effectiveness of a

catalyst particle increases with decreasing
activity !!

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 Operational challenges in solid-catalysed reactors

• Temperature: risk of hotspots and runaway of reactions

• Intermediate cooling of the fluid
• Equalisation of heat distribution throughout catalyst

Solid-catalysed reactors (2)
• Deactivation → design & operation must anticipate to a flexible maintenance!
• “N+1” design: close 1 compartment whilst N compartment in operation
• Accessibility: access doors & “manholes”, spaces inside the reactor, …
• Sufficient space for exchange of parts and catalytic elements in the reactor
• Dynamic operation to keep up continuous operation with cata deactivation

Solutions: Catalyst compartmentation, fluid and/or catalyst recycling, counter-current

flow operation (solid-fluid), continuous regeneration of catalyst, adaptive control, …

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Design: examples packed-bed catalytic reactors Design: examples fluidized-bed catalytic reactors

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Design: examples fluidized-bed catalytic reactors Operation: Staged packed-bed catalytic reactors
3 operation variables can be manipulated:
incoming temperature Ta, m% of cata in
rA,1 rA,2 first reactor, and amount of heat Qout

r’equilib=0
1

For a fixed (=intended) value of XA2

r’A,2 and total a given total mass of cata
we need to find an acceptable
combination (Ta, m%1, Qout)
r’A,1

r’A,1 > r’A,2 > r’equilib

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Operation: Staged mixed-flow catalytic reactors Operation: Staged p-b catalytic reactors with recycling
4 operation variables can be manipulated:
incoming temperature Ta, m% of cata in
first reactor, and amount of heat Qout and R

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Operation: “Cold shot” cooling Operation: Which scheme to use when ?
Useful for reactions that require large
preheating of incoming feed

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Operation: impact of catalyst deactivation

Constant flow

Constant XA

Constant FA

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