Solid Catalysts in Relation With The Reactor: Fixed-Bed Catalysts Moving-Bed Catalysts Slurry-Reactor Catalysts

Solid Catalysts in relation with the Reactor
Fixed-bed catalysts
relatively large particles (several mm)
mechanical strength important (fines formation)
Moving-bed catalysts
idem fixed-bed
spherical particles (to flow smoothly)
Slurry-reactor catalysts
powders (25 m)
attrition resistance important
usually high density important (for easy settlling)
Fluidised-bed and entrained-flow reactor catalysts

powders (20 - 200 m); well-controlled size distribution
attrition residence important
Structured catalytic reactors, e.g. monoliths

Catalysis and Catalysts - Manufacture
Shapes of Industrial Catalysts
Irregular granule
Sphere
Pellet
Ring
Minilith
Wagon wheel
Monolith
ceramic
Monolith
metallic
Foam
Extruded
cylindrical
Trilobe
Surface-volume ratio a
Mechanical strength
Pressure drop
Pore-diffusion resistance
Manufacture methods; costs
Comparison of Catalyst Shapes

Spheres
Low manufacturing costs

Relatively high pressure drop
Large diffusion length
Hydrodesulphurisation
Methanation
Impregnated noble-metal
Granules
Not common
Low-surface-area catalysts
Ammonia synthesis
Silver cat. For formaldehyde
Pellets
Regular shape; Most common

Good mechanical strength
Carbon monoxide shift

Hydrogenation
Extrudates
Low pressure drop; Common

Poor strength
Hydrodesulphurisation
Rings
High strength; Low pressure drop

Small diffusion length
Steam reforming
Ethylene oxide production
Monoliths
Low pressure drop; Insensitive to

dust; Small diffusion length
Exhaust gas cleaning
Gauzes
Low-surface-area catalysts
Ammonia oxidation
Other high-T processes
Pt Gauze
Reactor with gauze
SEM images
New
Used
Monoliths
Catalysis surface phenomenon

Particles should be small
Specific Surface Area (m2/g)
Specific Surface Area for Ni
Crystalline Size, d (nm)

Examples of Catalyst Manufacture

Mo salt
Fe salt
Precipitation
gelling
Silicate
Acid
Formation
clear sol
Ni-Al alloy
Melting
Cooling
Drying
Gelling
Crushing
Grinding
Water wash
Screening
Hydrothermic treatment
Ripening
Drying
Leaching (pH ~ 14)
Drying
Pelleting
Calcining
Fe-moylbdate
SiO2
Raney Nickel
Catalyst Preparation
Bulk catalysts
Supported catalysts
Suports
Silica
Alumina
Zeolites
Activated Carbon
Attachment of active phase
Co-precipitation
Impregnation
Deposition-precipitation
Chemical vapour deposition (CVD)
Sol-gel method
Raney Nickel
Porous Nickel
Start with alloy of Ni and Al
Mixing
Pros
Porous Ni
Melting
High activity
Cooling
High settling rate
Crushing
Cons
Regeneration difficult
Screening
Exposure to NaOH
solution (pH ca. 14
Unsatisfactory reproducibility
Pyrophoric
Ammonia Synthesis Catalyst

Fusion Route
iron-ore
H2, diluted O2
electric furnace
undersized
particles
reduction
passivation
casting table
screen
crushing
stabilized catalyst
Catalyst Supports
Function
carrier active phase
stabilizes active phase
access to active sites
Important properties
stability at reaction conditions
stability at regeneration conditions
texture (surface area, pore structure)
active phase support interaction
inert/reactive
heat capacity
thermal conductivity
shape,size
mechanical strength
cost
Catalysts Supports and Applications

Alumina
Hydrogenation, dehydrogenation, hydrotreating, hydrocracking,

FCC, reforming, isomerisation, car exhaust treatment,
methanol synthesis, low-temperature CO shift, steam reforming,
methanation, selective oxidation, alkene methathesis
Silica
Polymerisation, hydrogenation, oxidation, hydrodemetallisation
Silica-alumina
Ammoxidation, dehydrogenation
Zeolites
FCC, hydrocracking, isomerisation, cyclisation, dewaxing,

methanol-to-gasoline process, light alkanes-to-aromatics,
organic synthesis
Catalysts Supports and Applications

Diatomaceous earth
SO2 oxidation, hydrogenation
Clays
Hydrogenation, condensation
Cordierite monoliths
Car exhaust, after-burning
Activated carbons
Oxychlorination, hydrogenation (fine chemicals)
Titania
Selective oxidation, SCR
Magnesium aluminate
Steam reforming, methanation, methanol synthesis
Production of Silica (Porous SiO2)

Manufacturing route??
Raw material??
Start from solution Na-silicate
H+
Polymerisation
O-O Si OO-
SiO44-
O-
O-
O-
-O Si O Si O Si OOOO-
Si3O108-
dependent on pH
Gelation
Washing, Drying
O-
O-
-O Si O Si OOO-
Si2O76-
Production of Silica (Porous SiO2)

O-
Silicate anions
O-
-O Si OO-
O-
O-
-O Si O Si O Si OOOO-
O-
-O Si O Si OOO-
Si3O108-
SiO44-
Si2O76-
Formation of silanol groups

-O-Si-O- + H+
-O-Si-OH
Generation of Si-O-Si bonds

-O-Si-OH + -O-Si-OFormation of ring structures
-O-Si-O-Si-O + OHO-
O-
-O Si O Si OO
-O Si O Si OOO-
O-
Si4O128Four-ring
Formation of Silica Particles
OH
OH
HO Si OH
HO Si OH
1
OH
monomer
OH OH OH OH OH OH
OH
OH
OH
Si
Si
Si
Si OH
Si
2
O O O O O O O
O
O
O
following
HO Si OH polymerization
OH
+ H2O
dimer
particle of silica polycondensate
Colloidal solution (sol)

pH determines stability
Formation of Gels: Sol-Gel Method

Colloidal solution
Solution of micelles
pH ??
Surface charge depends on pH
Gel
(Hydro) gel
pH < 4
-Si-OH2+
pH > 9
-SiO -
Porous structures can be formed at pH 6 - 7

-Si-OH + -O-Si-OH
-Si-O-Si- + OH-
Silica Production Process

Silicate
Acid
Mixing
Washing
Drying
Classification
Packaging
Milling
Drying
Critical step
pores collapse, porosity reduced

capillary forces cause compression
Can this be prevented?

dry under supercritical conditions
exchange water for less polar fluid (e.g., alcohol)
OH
Surface structure after drying?
OH
OH
OH
-O Si O Si O Si O Si OO
at low Temperature : concentration silanol groups high

hydrophilic
at high Temperature: concentration of silanol groups low

hydrophobic
Fumed Silicas
SiCl4 + 4 H2 + O2
SiO2 + 4 HCl
To HCl absorption
Hydrogen
Oxygen (air)
Cyclone
Mixer
Burner
Vaporiser
Silicon tetrachloride
Cooler Deacidification
Hydrophilic, hydrophobic?
Particle size?
Pyrogenic
silica
Production of Alumina (Porous Al2O3)

Al is amphoteric
low pH, soluble
solution of Al2(SO4)3
high pH, soluble

solution of Al(OH)3
base
precipitate
acid
precipitate
Precipitation Regions of Aluminium Compounds

Al-oxide amphoteric
Soluble at low and high pH
solubility
10
12
14
Crystallized
hydrargillite
Crystallized bayerite
plus amorphous material
dependent on conditions
Poorly crystallized
pseudo boehmite
Several precipitates,
Amorphous precipitate
AlO2-
Region of
precipitation
Al3+
pH
Formation of Different Aluminas

Na-aluminate solution
Na2O.Al2O3
pH > 12
+
Acid
Al-sulphate solution
Al2O3.3 SO3
pH < 2
+
Base
at 3 < pH < 6
precipitation of
microcrystalline boehmite gel
AlO(OH)
at 6 < pH < 8
precipitation of
crystalline boehmite gel
AlO(OH)
Heating above 770 K

Amorphous Al2O3
at 8 < pH < 11
precipitation of
bayerite gel
Al(OH)3
aging at pH 8 and 353 K
gibbsite gel
Al(OH)3
aging at high pH
-Al2O3
-Al2O3
spinel structure: cubic close packing
-Al2O3
Heating at 1170 - 1270 K

-Al2O3
-Al2O3
Heating above 1370 K
a-Al2O3
corund structure: hexagonal close packing
a-Al2O3
Dehydration of Alumina upon Heating
H H H H H H
O
O
O
H
O
H
O
Chemically
bonded H2O
H
O
O Al O Al O Al
O
H
O
H
O
H
O
O Al O Al O Al
O
O+
+
O Al O Al O Al
O
Applications of Alumina
Alumina
Application
-alumina
hydrotreating
hydrocracking
methanation
reforming
hydrogenation
-alumina
isomerisation
-alumina
car exhaust
-alumina
steam reforming
ethylene oxidation
Bulk catalysts
Supported catalysts
Supports
Silica
Alumina
Zeolites
Activated Carbon
Co-precipitation
Impregnation
Sol-gel method
Catalyst Supports
Function
carrier active phase
stabilizes active phase
access to active sites
Important properties
stability at reaction conditions
stability at regeneration conditions
texture (surface area, pore structure)
active phase support interaction
inert/reactive
heat capacity
thermal conductivity
shape,size
mechanical strength
cost
Pore Volume Distributions

0.10
0.5
-Alumina
Wide-pore Silia
0.4
dV /dd (ml/g/nm)
dV /dd (ml/g/nm)
0.08
0.06
0.04
0.02
0.3
0.2
0.1
0.00
0.0
1
10
d pore (nm)
100
1000
0.010
100
1000
ZSM-5
dV /dd (ml/g/nm)
dV /dd (ml/g/nm)
d pore (nm)
10
-Alumina
0.008
10
0.006
0.004
8
6
4
2
0.002
0.000
1
10
100
d pore (nm)
1000
0.0
0.5
1.0
d pore (nm)
1.5
2.0
Early Zeolite Synthesis Method
Alumina
Alkali Hydroxide
Gel
373 K
Zeolite
Silica
Industrial Production of Na Aluminosilicate Zeolite
NaOH
Al-source
H2O Si-source
vapour
fresh
water
Product to
drying and
crushing
Mixing vessels
Belt conveyer
slurry
vapour
slurry
Crystallisation
concentrated mother liquor
Template
Quaternary alkyl-ammonium compounds
Ion-Exchange of Zeolite Y for Na Removal

NaY sieve
NH4+
1st
Exchange
Filtration &
washing
Na+
solution
Heating
NH4+
2nd
Exchange
Filtration &
washing
Final
drying
Na+
solution
Preparation of H-Zeolite from Na-Zeolite
H+
H+
Structure of Fe-ZSM5
FeAlOx
(FeO)n
Fe
Fe
Fe
liu
m
ne
on
ar
go
kr n
yp
to
n
xe
no
m
et n
ha
n
et e
ha
pr ne
op
an
bu e
ta
n
et e
hy
n
et e
he
pr ne
op
e
1- ne
bu
is ten
ob e
ne uta
op ne
en
is tan
oe
cy oc
ta
cl
op ne
cy rop
a
cl
oh ne
ex
a
be ne
nz
e
p- ne
xy
le
o- ne
xy
l
am ene
m
( C o ni
4H a
9
(C )3N
4F
9)
3N
w
at
ca
rb hyd er
on ro
m ge
ca on n
o
rb
on xid
di e
ox
id
ox e
yg
ni en
tr o
ge
n
he
Kinetic diameter [nm]
Kinetic Diameters of Molecules

Compared with Zeolite Pore Size
0.8
0.2
Zeolite-X, Y
0.6
ZSM-5
0.4
Zeolite-4A
Solid-State Reactions in Y Zeolite During Steaming
Si
O
Si
O Al O Si
Si
H2O
OH
Si OH
HO Si
OH
Si
Si
Si(OH)4
Non-framework
species
H2O
From other parts of the lattice
(creating meso-pores)
Si
O
Si
O Si O Si
O
Si
+ Al(OH)3
Zeolites Classified by their Si/Al Ratio

Si/Al Ratio
Zeolite
Properties
Low (1-1.5)
A, X
Relatively low stability of framework

Low stability in acids
High stability in bases
High concentration of acid groups
with moderate acid strength
Hydrophilic
Intermediate (2-5)
Erionite
Chabazite
Clinoptilolite
Mordenite
Y
ZSM-5a
Erionitea
Mordenitea
Ya
High (~10 to )
a Catalysis and Catalysts - Manufacture
Relatively high stability of framework

High stability in acids
Low stability in bases
Low concentration of acid groups
with high acid strength
Hydrophobic
Trends in Catalytic Cracking Catalyst Performance
Zeolite Applications
Catalysts 14%
Adsorbents 8%
Desiccants
Natural
11%
zeolites
Detergents 67%
Activated Carbon
Carbonaceous material
High T
Pyrolysis
peat, coal, biomass, sugar,

polymers
Porous material
H2O
Partial gasification
Additional porosity
Activated carbon
Structure of Activated Carbon from Wood
Functional Groups
+ H2O, OHO
O
O
O+ H-
+ OH-, HO
O
O
+ HOH
+ OH-
+ H2O, OHO
O +H
O
+ H-
O
O + H-
OH
+ OH-
Reactions with Carbon-supported

Catalysts
Reaction
Active Phase
Hydrogenations
Pt, Pd, Ni
Acetylene + HCl to vinyl chloride
HgCl2
Acetylene + HAc to vinyl acetate
Zn(OCOCH3)2
Activated Carbons
Positive
stable at all pH, T
high adsorption capacity
wide variety textural properties
"soft" ligand
not much erosion pumps, etc
inert
Negative
chemical reactivity (O2,.)
mechanically weak
fines (separation)
Carbon-based Monolith Support
a.
b.
monolithic
structure
carbon
Carbon-coated monolith
Integral-type carbon support
Bulk catalysts
Supported catalysts
Supports
Silica
Alumina
Zeolites
Activated Carbon
Co-precipitation of support and active phase
Impregnation
Sol-gel method
(Co)Precipitation
Coprecipitation
mixed oxides
supersaturated solution
nucleation
growth
homogeneous or
heterogeneous
Parameters
nature salts
cA,cB,...
T , pH
ripening time
nucleation promotors
.......
Synthesis of HTlcs
pHC
pH = 9.5
T = 22C
TC
CO32-/Al3+ = 2
NaOH+Na2CO3
pH
M2+/M3+ = 3
Metal nitrates
(1.5 M)
Aging @65C for 18 h (reflux)

Washing (water @30C) and filtering
Drying
[Ni6Al2 (OH-)16][OH-,CO32-]4H2O
Production of Catalysts by Precipitation
Structure hydrotalcites (HTlcs)

a
M2+
M3+
... anionic clays or

layered double
hydroxides
OH-
c
+
interlaye
r space
XnH2O
brucitelike layer
Adsorbent, flame retardant,

ion-exchanger, antiacid,
[M2+1-xM3+x(OH-)2][Xn-]x/nmH2O
catalyst precursor and support
Catalysts Prepared by Coprecipitation

Reaction
Catalytic elements
Catalysts
Hydrogenation
Ni/Al
Steam reforming
Ni/Al, Ni/Mg/Al
Methanol synthesis
Cu/Zn/Al, Zn/Cr, Cu/Zn/
Higher Alcohol Synthesis
Cu/Co/Zn/Al, Cu/Co/Zn/
Fischer-Tropsch
Co/Cr, Fe/Al
Supports for catalysts

Basic support
Mg/Al
Coprecipitation
Positive
components well
mixed on an atomic
scale
high loading possible
at high loadings
relatively high
dispersion
high thermostability
Negative
difficult scale-up
at low loadings
relatively low dispersion
Impregnation
Wetting of (preshaped) support with solution precursor
"Wet"
Excess solution
"Dry"
Amount of solution=Pore Volume
Drying
Critical, tendency towards "egg-shell" catalyst
Calcination
Critical
bursting support
interaction compounds
sintering
Relation between PZC and Surface Charge

Lower pH
H H+
O
Si
pH = PZC
H H+ H H+
O
O
H
O
O Si O Si
Si
H
O
Higher pH
H
O
O-
O Si O Si
Si
pH
pH < PZC
pH = PZC
pH > PZC
Surface Charge
positive
neutral
negative
Species
MOH2+
MOH
MO-
Adsorption
anions
pH increase
O-
O-
O Si O Si
PZC
cations
Alumina
8-9
Silica
~3
10% Alumina/Silica ~ 5
Adsorption from [Pt(NH3)4]2+ solution
Silica gel
-Alumina
Processes during Impregnation
Solution flow into pores
adsorption
Adsorption/desorption + diffusion
Drying
diffusion
adsorption
evaporation
Active-Phase Distributions
Uniform
Egg-shell
Egg-white
DRYING!
Viscosity precursor!
Egg-Yolk
Impregnation of -Alumina with Pt

OH
2 Al
PtCl62-
Cl Cl
Cl Pt Cl
O O
4-
+ 2 HCl
Al Al
Competitive adsorption reduces time

Impregnation of -Alumina with Pt

Influence of Coadsorbing Ions
Empty (OH)
Empty (OH)
Citric acid
Increasing acid concentration

Pt/Al2O3
Al2O3
Citric acid
FeCl3 - local accumulations

Tendency
to
crystallization
(NH4)2Fe(SO4)2
NH4 Fe EDTA
pH = 5.3
NH4 Fe EDTA
pH = 10
Bare SiO2
support
Fe gluconate (transparent)
Catalyst Preparation by Impregnation
Wet impregnation
Dry impregnation
Impregnation of Monoliths with Ni

Influence of Drying Method
a.
Conventional
drying
b.
Forced-flow
drying
c.
Microwave
drying
d.
e.
Freeze drying
1h
24 h
Homogeneous Deposition Precipitation
Peristaltic Pump (Gilson Minipuls)

Injection Speed 50 mL/h
pH Electrode
pH
Time
2 g/L NaOH
SiO2
Ni(NO3)2.6H2O
2g /2L
0.5 g / 2 L
Homogeneous Deposition Precipitation
Applicable in precipitation upon increasing pH

example: Ni2+
Ni(OH)2
Upon heating (370 K) urea in water decomposes slowly:
CO(NH2)2 + 3 H2O
CO2 + 2 NH4+ + 2 OH-
pH increases slowly throughout particle

homogeneous loading
La(NO3)3
PdCl2
{Pd(OH)2}n
O-Pd-OH
A.
SiO2
O-Pd- OH
O-Pd-OH
{La(OH)3}n
{PdLax(OH)y}n
O-La-OH
O-La-O-Pd-OH
O-La-O-Pd-OH
SiO2
B.
OH
Pd
O
SiO2
SiO2
La2O3
Figure 6 of Preparation of lanthanum promoted Pd catalysts

OH
La
O
Pd
O
C.
Chemical Vapour Deposition

Volatile precursors deposited in cold zone
Example:
Ni-Cu Alloy synthesis
Synthesize copper via impregnation and reduce to metallic
Deposit Ni(CO)4 afterwards
Carbonyl decomposes preferentially on copper particles
Oil-Drop Coagulation
Sol
Distributor cone
Oil overflow
to
recirculation
Organic phase
Oil inlet
Water inlet
Aqueous
phase
Product to
ripening, washing
and drying

Solid Catalysts in Relation With The Reactor: Fixed-Bed Catalysts Moving-Bed Catalysts Slurry-Reactor Catalysts

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Solid Catalysts in Relation With The Reactor: Fixed-Bed Catalysts Moving-Bed Catalysts Slurry-Reactor Catalysts

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Solid Catalysts in relation with the Reactor

Fluidised-bed and entrained-flow reactor catalysts

Structured catalytic reactors, e.g. monoliths

Shapes of Industrial Catalysts

Catalysis and Catalysts - Manufacture

Comparison of Catalyst Shapes

Low manufacturing costs

Regular shape; Most common

Carbon monoxide shift

Low pressure drop; Common

High strength; Low pressure drop

Low pressure drop; Insensitive to

Exhaust gas cleaning

Catalysis and Catalysts - Manufacture

Catalysis and Catalysts - Manufacture

Catalysis and Catalysts - Manufacture

Catalysis surface phenomenon

Specific Surface Area (m2/g)

Specific Surface Area for Ni

Crystalline Size, d (nm)

Examples of Catalyst Manufacture

Catalysis and Catalysts - Manufacture

High settling rate

Catalysis and Catalysts - Manufacture

Ammonia Synthesis Catalyst

Catalysis and Catalysts - Manufacture

Catalysis and Catalysts - Manufacture

Catalysts Supports and Applications

Hydrogenation, dehydrogenation, hydrotreating, hydrocracking,

Polymerisation, hydrogenation, oxidation, hydrodemetallisation

FCC, hydrocracking, isomerisation, cyclisation, dewaxing,

Catalysis and Catalysts - Manufacture

Catalysts Supports and Applications

SO2 oxidation, hydrogenation

Car exhaust, after-burning

Oxychlorination, hydrogenation (fine chemicals)

Selective oxidation, SCR

Steam reforming, methanation, methanol synthesis

Catalysis and Catalysts - Manufacture

Production of Silica (Porous SiO2)

Start from solution Na-silicate

Production of Silica (Porous SiO2)

Formation of silanol groups

Generation of Si-O-Si bonds

Formation of Silica Particles

particle of silica polycondensate

Colloidal solution (sol)

Catalysis and Catalysts - Manufacture

Formation of Gels: Sol-Gel Method

Surface charge depends on pH

Porous structures can be formed at pH 6 - 7

Silica Production Process

pores collapse, porosity reduced

Can this be prevented?

Surface structure after drying?

at low Temperature : concentration silanol groups high

at high Temperature: concentration of silanol groups low

Catalysis and Catalysts - Manufacture

Production of Alumina (Porous Al2O3)

high pH, soluble

Catalysis and Catalysts - Manufacture

Precipitation Regions of Aluminium Compounds

Soluble at low and high pH