Activity, Selectivity, Stability

Which property most important?

In process development, which one is easily measured?

Catalysis and Catalysts - Activity, Selectivity and Stability

Catalyst Selectivity
Synthesis gas applications

CH3OH

CH4
Ni

Cu
H2 / CO

Fe, Co
CnH2n+2
CnH2n
Catalysis and Catalysts - Activity, Selectivity and Stability

Cu + Co
CnH2n+1OH
(n = 1 - 6)

Examples of Catalyst Deactivation

1.0

CH3OH

p
= 70 bar
GHSV = 35000 h-1
T
= 515 K

FCC

0.8
r (rel)

Methanol Yield (gcm-3h-1)

CO + 2 H2

0.6
0.4
0.2
0.0

Methanol Synthesis

12

15

Time (h)
0

500

1000

Time (h)
a

k1.85 (gcm-3h-1%S-0.85)

HDS
S-344 (660 K)

S-324 (655 K)
0
0

Catalysis and Catalysts - Activity, Selectivity and Stability

1000
Time (h)

1800

Catalytic Reforming (Gasoline Production)

Conversion (% olefins/initial paraffins)

C12H26
pH
2
pHC
LHSV
T

30

C12H24 + H2

= 1.35 bar
= 0.10 bar
= 1 h-1
= 745 K

Deactivation due to
coke deposition

Catalyst Pt (0.2%) / Al2O3

20
+ 0.17% W
+ 0.17% Re
+ 0.04% Ru

10

+ 0.04% Ir
Pt only
0

100

200

Time (h)
Catalysis and Catalysts - Activity, Selectivity and Stability

Alloying quite successful

Time-Scale of Deactivation
10 -1

10 0

10 1

10 2

10 3

10 4

10 5

10 6

10 7

10 8

Hydrocracking
HDS
Catalytic reforming

FCC

Most bulk
processes
0.1-10 year

EO
MA
Formaldehyde
Aldehydes
Hydrogenations
Acetylene
Oxychlorination

C3 dehydrogenation

Batch
processes
hrs-days

Fat hardening
NH3 oxidation
SCR

Time / seconds
-1

10

10

TWC
1

10

10

10

10

10

1 hour 1 day
Catalysis and Catalysts - Activity, Selectivity and Stability

10

10

10

1 year

Deactivation of catalysts
irreversible loss of activity
Types of deactivation
Poisoning
strong chemisorption of impurity in feed
(Inhibition: competitive adsorption, reversible)
Fouling
secondary reactions of reactants or products,coke formation
Thermal degradation
sintering (loss of surface area), evaporation
Mechanical damage
Corrosion / leaching

Catalysis and Catalysts - Activity, Selectivity and Stability

Types of Deactivation

Selective poisoning
Fouling

S
S

Non-selective poisoning

Catalyst
particle

Fine

Attrition
Sintering
= active site
= support

Leaching

Catalysis and Catalysts - Activity, Selectivity and Stability

= component in reaction medium

What are poisons?

Strong
chemisorber

H2S on Ni
NH3 on Si-Al

Surface active
metal or ion

Cu on Ni
Ni on Pt
Pb or Ca on Co3O4
Pb on Fe3O4

High M.W.
product
producer

Fe on Cu
Fe on Si-Al
from pipes
acetylenes
dienes
from feed
or product

Catalysis and Catalysts - Activity, Selectivity and Stability

Sintering
accelerator

H2O (Al2O3)
Cl2 (Cu)

Typical Stability Profiles in Hydrotreating

II
activity

coke

metals

III
Amount of poisoning

Catalytic activity

Time on Stream

Initially high rate of deactivation

mainly due to coke deposition
Subsequently coke in equilibrium
metal deposition continues
Catalysis and Catalysts - Activity, Selectivity and Stability

Influence of Pore Size on Vanadium Deposition

Hydrotreating of Heavy Feedstock

Deposited vanadium

Wide-pore catalyst

Narrow-pore catalyst

Outside

Centre

Outside

Radial position in catalyst pellet

Catalysis and Catalysts - Activity, Selectivity and Stability

Carbon Filaments due to CH4 Decompostion

873 K, Ni/CaO catalyst

Catalysis and Catalysts - Activity, Selectivity and Stability

Carbon Formation on Supported

Metal Catalyst

C
H2

CnHm
H H

Metal crystallite

Catalysis and Catalysts - Activity, Selectivity and Stability

Support

Growing
fillament

Sintering of Alumina upon Heating

SBET (m2/g)

Sintering

Reduction of surface area

Tcalc (K)
Catalysis and Catalysts - Activity, Selectivity and Stability

Sintering of Supported Catalysts

monomer dispersion

2-D cluster

3-D particle

vapour

particles migrate

surface

coalesce
interparticle transport

migrating
metastable

Dependent on:
carrier properties

stable

temperature
composition of bulk fluid
.

Catalysis and Catalysts - Activity, Selectivity and Stability

Predictable?

THttig and TTamman

Sintering is related to melting
THttig : defects become mobile
Ttamman: bulk atoms become mobile
Purification (Cl removal) required in Water-Gas-Shift (supported Cu)??
Sintering to be expected in three way-catalysis (supported Pt-Rh) ??

Tmelting

THttig

Ttamman

Pt

2028

608

1014

678

PtO

823

247

412

480

800

PtCl2

854

256

427

268

447

Rh

2258

677

1129

Rh2O3 1373

312

687

Tmelting

THttig

Ttamman

Al2O3

2318

695

1159

Cu

1356

407

CuO

1599

CuCl2

893

Catalysis and Catalysts - Activity, Selectivity and Stability

Deactivation due to Mechanical Damage

during transport, storage, packing, use
loading in barrels, unloading, packing of reactor
in reactor: weight of column of particles
attrition in moving systems (fluid beds, moving beds)

during start-up, shut-down
temperature variations (thermal shocks)
chemical transformations
sulphiding, reduction
regeneration: high T, steam

Catalysis and Catalysts - Activity, Selectivity and Stability

Corrosion / Leaching

Alumina
dissolves at pH > 12 and pH < 3,
so close to these pH-values corrosion and leaching
use carbon instead at very low or very high pH

Sulphiding of oxides in the presence of H2S

Liquid-phase catalysis
in heterogenisation of homogeneous catalysts activity often
due to the leached compounds rather than the solid phase
in solid-catalysed fat hydrogenation traces of the Ni catalyst
appear in the product; with Palladium this is not the case

Catalysis and Catalysts - Activity, Selectivity and Stability

Influence of Deactivation on Reaction Rate

conversion
or
kobs

initial level

process time

k obs = k intr NT
constant

variable

variable
blocking of pores

loss of surface area

Fouling

loss of active sites

Sintering
Catalysis and Catalysts - Activity, Selectivity and Stability

Poisoning

Deactivation - depends on?

Poisoning
chemisorption on active sites
reversible or irreversible

Selective poisons: Modifiers

block side reactions
inhibit consecutive reactions
(kinetics)
feed & process conditions

feed conditions

process conditions
Mechanical deactivation
loss of catalytic material
due to attrition/abrasion
loss of surface area due
due to crushing
irreversible

kobs

Fouling
physical blockage of surface
by carbon or dust
usually regenerable
feed & process conditions
process conditions

process conditions
Leaching
loss of active phase, e.g. by
dissolution in reaction medium
most common in liquid phase
often reversible

Catalysis and Catalysts - Activity, Selectivity and Stability

Sintering
loss of surface area
gradual or catastrophic
usually irreversible

Heat

Stability too low; What to do?

Understand the cause of deactivation

Take logical measures
at catalyst level
sound reactor and process design
good engineering practice

Catalysis and Catalysts - Activity, Selectivity and Stability

Catalyst Level

improvement of active phase or support
e.g. use titania instead of alumina in SCR

optimisation of texture
use wide-pore catalyst in HDM to prevent pore blocking

profiling of active phase
e.g. egg-yolk profile will protect active sites against
poisoning and fouling if these are diffusion-limited and the
reaction is not

reduce sintering by structural promoters or stabilisers

make catalyst more attrition resistant
encapsulation of active material in porous silica shell
increases attrition resistance without influencing activity
Catalysis and Catalysts - Activity, Selectivity and Stability

Tailored Reactor and Process Design

Time-scale of deactivation dominant
years

fixed-bed reactor;
no regeneration

months

fixed-bed reactor;
regeneration while reactor is off-line

weeks

fixed-bed reactors in swing mode, moving-bed reactor

minutes - days

fluidised-bed reactor, slurry reactor;

continuous regeneration

seconds

entrained-flow reactor with continuous regeneration

Catalysis and Catalysts - Activity, Selectivity and Stability

Different Engineering Solutions

allowing for Regeneration
Propane dehydrogenation - deactivation by coke formation
Adiabatic moving-bed reactors (Oleflex)

Parallel adiabatic fixed-bed reactors (Catofin)

Feed

Feed
Regenerator

Fired
heaters

Air
Air
Product
catalyst

Reactors

Reactors in operation

Regeneration circuit

Product

Tubular fixed-bed reactors in furnace (STAR)

Fluidised-bed reactor and regenerator (FBD-4)

Product

Fuel
Air
Flue gas

Flue gas
Regen.
catalyst

Multiple tubular
reactors

Furnace

Steam
Feed

Catalysis and Catalysts - Activity, Selectivity and Stability

Product

Feed

Spent
catalyst
Reactor

Fuel
Air
Regenerator

Good Engineering Practice

Feed purification for removal of poisons
upstream reactor
poison trap inside reactor on top of catalyst
overdesign of reactor if catalyst itself is poison trap

Optimisation of reaction conditions
use of excess steam in steam reforming decreases coke
deposition
catalyst deactivation in selective hydrogenation of CCl2F2
strongly increases above 500 K operate below 510 K

Optimisation of conditions as function of time-on-stream
compensate for activity loss by increasing T with time
Catalysis and Catalysts - Activity, Selectivity and Stability

Examples
Process

Catalyst

Main deactivation
mechanism

Time scale of
deactivation

Consequences for
catalyst

Regeneration

Consequences for process

FCC

zeolite

Coke

Regeneration on s scale

Coke combustion

Recirculation catalyst between

reactor and regenerator

Oxidative
dehydrogenation

various oxides

Coke

idem

Catalytic
reforming

Pt/-Al2O3

Coke, Cl loss

months
days

Alloying

Coke combustion
Cl supply
redispersion

Fixed bed, swing operation, moving

bed

Hydrotreating

Co/Mo/S/Al2O3

Coke
metal sulphides

months
days

Once-through catalyst
Adapted porosity

Coke combustion

Fixed bed, slurry, moving bed

Methanol

Cu/ZnO/Al2O3

Sintering (Cl)

Stabilization

Feed purification

Water-gas shift

Cu/ZnO/Al2O3

Poisoning (S, Cl)

Stabilisers (ZnO)

Feed purification

Three-way
catalyst

Pt, Pd

Sintering, loss of active

components, deposits
(Zn, P from lubricants)

Noble metals, stabilized

alumina (La, Ba)

Rejuvenation by
leaching

Steam reforming

Ni/Al2O3

Coke, whiskers

K, Mg gasification
catalysts

Coke combustion

Excess steam

Dry reforming

Ni

coke

S-doping

Coke combustion

Excess steam

Diesel soot

Cu-Cl

evaporation

min , h

Select other catalyst

DeNOx

V2O5/Al2O3

Formation surface salts

months

Select other carrier

Wacker oxidation

Pd, Cu

Catalyst deposit

Xylene oxidation

Co, Mo, Br

Mo,Co deposits

Add new catalyst

Styrene

Iron oxide

Coke, sintering
movement promoters

Structural promoters

Catalysis and Catalysts - Activity, Selectivity and Stability

Similar schemes as in FCC

Add catalytic additives to fuel (Ce)

Low pH
Deposits in reactor and downstream
Coke gasification
in steam