Solid Catalysts by Reactor

w Fixed-bed catalysts
– relatively large particles (several mm)
– mechanical strength important (fines formation)
w Moving-bed catalysts
– idem fixed-bed
– spherical particles (to flow smoothly)
w Slurry-reactor catalysts
– powders (25 m)
– attrition resistance important
– usually high density important (for easy settling)
w Fluidised-bed and entrained-flow reactor catalysts
– powders (20 - 200 m); well-controlled size distribution
– attrition residence important
w Structured catalytic reactors, e.g. monoliths

Catalysis and Catalysts - Manufacture

 Shapes of Industrial Catalysts

Irregular granule Sphere Pellet Extruded

cylindrical

Ring Minilith Wagon wheel Trilobe

Surface-volume ratio a’
Mechanical strength
Monolith Monolith Foam Pressure drop
ceramic metallic Pore-diffusion resistance
Manufacture methods; costs

Catalysis and Catalysts - Manufacture

 Comparison of Catalyst Shapes
Spheres Hydrodesulphurisation Low manufacturing costs
Methanation Relatively high pressure drop
Impregnated noble-metal Large diffusion length

Granules Ammonia synthesis Not common

Silver cat. For formaldehyde Low-surface-area catalysts

Pellets Carbon monoxide shift Regular shape; Most common

Hydrogenation Good mechanical strength

Extrudates Hydrodesulphurisation Low pressure drop; Poor strength

Rings Steam reforming High strength; Low pressure drop

Ethylene oxide production Small diffusion length

Monoliths Exhaust gas cleaning Low pressure drop; Insensitive to

dust; Small diffusion length

Gauzes Ammonia oxidation Low-surface-area catalysts

Other high-T processes

Catalysis and Catalysts - Manufacture

 Pt Gauze
SEM images
Reactor with gauze

New

Used

Catalysis and Catalysts - Manufacture

 Monoliths

Catalysis and Catalysts - Manufacture

 Specific Surface Area for Ni

700

Specific Surface Area, SA (m2/g)

600

500

400

300

200

100

0
0 10 20 30 40 50
Crystalline Size, d (nm)

Catalysis and Catalysts - Manufacture

 Examples of Catalyst Manufacture
Mo salt Fe salt Silicate Acid Ni-Al alloy

Precipitation Formation Melting

gelling clear sol

Cooling
Drying Gelling

Crushing
Grinding Water wash

Screening
Hydrothermic treatment Drying
Ripening
Leaching (pH ~ 14)

Drying

Pelleting

Calcining

Fe-moylbdate SiO2 Raney Nickel

Catalysis and Catalysts - Manufacture

 Catalyst Preparation

w Bulk catalysts
w Supported catalysts
– Supports
• Silica
• Alumina
• Zeolites
• Activated Carbon
– Attachment of active phase
• Co-precipitation
• Impregnation
• Deposition-precipitation
• Chemical vapour deposition (CVD)
• Sol-gel method

Catalysis and Catalysts - Manufacture

 Raney Nickel

 Mixing

w Porous Ni
w
 Melting

w High activity
w
 Cooling

w High settling rate
w
 Crushing

w Regeneration difficult
w
 Screening

w Unsatisfactory reproducibility
w
 Exposure to NaOH
w Pyrophoric
 solution (pH ca. 14

Catalysis and Catalysts - Manufacture

 Ammonia Synthesis Catalyst
Fusion Route
iron-ore
H2, diluted O2
undersized
particles
electric furnace

reduction
passivation
casting table screen

crushing

Catalysis and Catalysts - Manufacture stabilized catalyst

 Catalyst Supports

wFunction wImportant properties

–carrier active phase –stability at reaction conditions
–stabilizes active phase –stability at regeneration conditions
–access to active sites –texture (surface area, pore structure)
–active phase support interaction
–inert/reactive
–heat capacity
–thermal conductivity
–shape,size
–mechanical strength
–cost

Catalysis and Catalysts - Manufacture

 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

Catalysis and Catalysts - Manufacture

 Catalysts Supports and Applications

Diatomceous 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

Catalysis and Catalysts - Manufacture

 Production of Silica (Porous SiO2)

 Start from solution Na-silicate




H+
 Polymerisation


 Gelation


 Washing, Drying

Catalysis and Catalysts - Manufacture

 Production of Silica (Porous SiO2)

O- O- O- O- O- O-
Silicate anions -O Si O- -O Si O Si O Si O- -O Si O Si O-
O- O- O- O- O- O-

SiO44- Si3O108- Si2O76-

Formation of silanol groups

-O-Si-O- + H+ -O-Si-OH

Generation of Si-O-Si bonds

-O-Si-OH + -O-Si-O- -O-Si-O-Si-O + OH-

Formation of ring structures O- O-

-O Si O Si O- Si4O128-
O O Four-ring
-O Si O Si O-
Catalysis and Catalysts - Manufacture

O- O-
 Formation of Silica Particle

OH
OH OH OH OH OH OH OH
OH Si OH
Si Si
OH HO Si OH
Si Si OH
1 2 O O O O O O O O
HO Si OH O O
following O
OH HO Si OH polymerization
OH + H2O

monomer dimer particle of silica polycondensate

Catalysis and Catalysts - Manufacture

 Formation of Gels: Sol-Gel Method

Colloidal solution Gel

Solution of micelles (Hydro) gel

pH ?? Surface charge depends on pH 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-
Catalysis and Catalysts - Manufacture
 Silica Production Process
Silicate Acid
Silicate Acid

Mixing

Washing Mixing

Drying
Washing
Drying
Milling

Classifi-
cation Classification Milling

Packaging
Packaging

Catalysis and Catalysts - Manufacture

 Drying

wCritical step
•capillary forces cause compression
•pores collapse, porosity reduced
wCan this be prevented?
•exchange water for less polar fluid (e.g., alcohol)
•dry under supercritical conditions
wAfter drying
•at low Temperature : hydrophilic
•at high temperature: concentration of silanol
groups low hydrophobic

OH OH OH OH
-O Si O Si O Si O Si O-
O O O O
Catalysis and Catalysts - Manufacture
 Fumed Silica’s

SiCl4 + 4 H2 + O2 SiO2 + 4 HCl

Hydrogen To HCl absorption

Oxygen (air)
Cyclone

Mixer

Burner

Vaporiser

Silicon tetrachloride Pyrogenic

silica
Cooler Deacidification

Catalysis and Catalysts - Manufacture

 Production of Alumina (Porous Al2O3)

Al is amphoteric

low pH, soluble high pH, soluble

solution of Al2(SO4)3 solution of Al(OH)3

base acid

precipitate precipitate

Catalysis and Catalysts - Manufacture

Precipitation Regions of Aluminium Compounds

Al-oxide amphoteric Soluble at low and high pH

solubility

Al3+ Region of AlO2-

precipitation

2 4 6 8 10 12 14 pH

Amorphous precipitate

pseudo boehmite

plus amorphous material

Crystallised
hydrargillite
Poorly crystallised

Crystallized bayerite
Several precipitates,
dependent on conditions

Catalysis and Catalysts - Manufacture

 Formation of Different Aluminas
Al-sulphate solution Na-aluminate solution
Al2O3.3 SO3 Na2O.Al2O3
pH < 2 pH > 12
+ +
Base Acid

at 3 < pH < 6 at 6 < pH < 8 at 8 < pH < 11

precipitation of precipitation of precipitation of
microcrystalline boehmite gel crystalline boehmite gel bayerite gel gibbsite gel
AlO(OH) AlO(OH) Al(OH)3 Al(OH)3

ageing at pH 8 and 353 K ageing at high pH

Heating above 770 K
Amorphous Al2O3 γ −Al2O3 η −Α l2O3 χ −Al2O3
spinel structure: cubic close packing
Heating at about 1170 - 1270 K

θ −Al2O3 δ −Al2O3 α −Α l2O3

Heating above 1370 K

α −Α l2O3
Catalysis and Catalysts - Manufacture corund structure: hexagonal close packing
 Dehydration of Alumina upon Heating

Chemically
H H H H H H bonded H2O
O O O H H H
H H H O O O O-
+ +
O O O O Al O Al O Al O Al O Al O Al
O Al O Al O Al O O O O O O
O O O

Catalysis and Catalysts - Manufacture

 Applications of Alumina
A lu m in a A p p lic a tio n
γ -a lu m in a h y d r o tr e a tin g
h y d r o c r a c k in g
m e th a n a tio n
r e f o r m in g
h y d r o g e n a tio n

η -a lu m in a is o m e r is a tio n

θ -a lu m in a car ex haust

α -a lu m in a s te a m r e f o r m in g

Catalysis and Catalysts - Manufacture

e th y le n e o x id a tio n
 Pore Volume Distributions
0.10 0.5
Wide-pore Silia  -Alumina
0.08 0.4
dV /dd (ml/g/nm)

dV /dd (ml/g/nm)
0.06 0.3

0.04 0.2

0.02 0.1

0.00 0.0
1 10 100 1000 1 10 100 1000
d pore (nm) d pore (nm)

0.010
10

0.008
 -Alumina ZSM-5
8
dV /dd (ml/g/nm)

dV /dd (ml/g/nm)
0.006 6

0.004 4

0.002 2

0.000 0
1 10 100 1000 0.0 0.5 1.0 1.5 2.0
d pore (nm) d pore (nm)

Catalysis and Catalysts - Manufacture

 Early Zeolite Synthesis Method

Alumina Alkali Hydroxide Silica

Gel
373 K
Zeolite

Catalysis and Catalysts - Manufacture

 Industrial Production of Na Aluminosilicate Zeolite

NaOH Al-source H2O Si-source

vapour
fresh
water
Product to
drying and
Mixing vessels crushing
Belt conveyer

slurry
vapour

slurry
Crystallisation
concentrated mother liquor

Catalysis and Catalysts - Manufacture

 Zeolite Applications

Catalysts 14%
Adsorbents 8%
Desiccants

Natural
11%
zeolites

Detergents 67%

Catalysis and Catalysts - Manufacture

 Kinetic diameter (nm)
Kinetic diameter [nm]

0
0.2
0.4
0.6
0.8
1
he
liu
m
ne
on
ar
go
kr n
yp
to
n
xe
no
m
et n
ha
n
et e
ha
pr n e
op
an
bu e
ta
n

Catalysis and Catalysts - Manufacture

et e
hy
n
et e
he
pr ne
op
e
1- ne
bu
is ten
o-
b e
ne ut a
o p ne
en
is tan
o- e
cy o c
cl ta
op ne
cy r o p
cl a
o h ne
ex
a
be ne
nz
e
p- ne
xy
le
o- ne
xy
l
am en e
m
(C oni
4H a
9
(C )3N
4F
9)
3N
w
ca at
rb hyd er
on ro
m ge
c a on n
rb o
on xid
di e
ox
id
ox e
Kinetic Diameters of Molecules

yg
ni e n
Compared with Zeolite Pore Size

tro
ge
n
ZSM-5

Zeolite-4A
Zeolite-X, Y
Preparation of H-Zeolite from Na-Zeolite

NH4+

> 570 K - NH3

Catalysis and Catalysts - Manufacture

 Ion-Exchange of Zeolite Y for Na Removal
NaY sieve
NH4+ or 1st
RE3+ Exchange
solution

Filtration &
washing Na+
solution

Heating

NH4+ or 2nd
Na+
RE3+ Exchange
solution
solution

Filtration &
washing

Final
drying
Catalysis and Catalysts - Manufacture
 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
High (~10 to ∝ ) ZSM-5 a Relatively high stability of framework
Erionite a High stability in acids
Mordenite a Low stability in bases
Ya Low concentration of acid groups
with high acid strength
Hydrophobic
a
By dealumination.
Catalysis and Catalysts - Manufacture
Solid-State Reactions in Y Zeolite During Steaming

Si Si
O OH
H2O
Si O Al O Si Si OH HO Si + Al(OH)3
O OH
Si Si
Si(OH)4
Non-framework
H2O species

From other parts of the lattice

(creating meso-pores) Si
O
Si O Si O Si
O
Si

Catalysis and Catalysts - Manufacture

Trends in Catalytic Cracking Catalyst Performance

(1946)

ts
ca
s
10 (1955)

ou
(1964)

ts
ph

ca
(1968-72)

or
9
Coke yield (wt% on FF)

am

s
ou
ts ing

ph
a
s k
in
8 ly c

or
cra
um ta

am
ca er
al

lite is
a +r -Y) (1980’s)
w

7 in
Lo

o -H
um

Ze lites (RE
al

o s
6 Ze l it e Y)
h

e o US
ig

ez ts (
H

c t i v c a
5
s e le c t iv e
sel e
oke k e
C
4 h l y co
Hig
50 60 70 80
Conversion (vol%)

Catalysis and Catalysts - Manufacture

 Activated Carbons

wPositive wNegative
–stable at all pH, T –chemical reactivity
–high adsorption capacity (O2,.)
–wide variety textural properties –mechanically weak
–"soft" ligand –fines
–not much erosion pumps, etc
–inert

Catalysis and Catalysts - Manufacture

 Activated Carbon

Carbonaceous material peat, coal, biomass, sugar,

polymers
High T
Pyrolysis

Porous material

H2O
Partial gasification

Additional porosity Activated carbon

Catalysis and Catalysts - Manufacture
Structure of Activated Carbon from Wood

Catalysis and Catalysts - Manufacture

 Functional Groups

+ H2O, OH- + OH-, H-

O O O O
- O-
+H
O

O
+ H- + H2O, OH-
OH O
+ OH-
O
OH
O O + OH-
O +H
- + H- O + H-

Catalysis and Catalysts - Manufacture

 Reactions with Carbon-supported
Catalysts

Reaction Active Phase

Hydrogenations Pt, Pd, Ni
Acetylene + HCl to vinyl chloride HgCl2
Acetylene + HAc to vinyl acetate Zn(OCOCH
3)2

Catalysis and Catalysts - Manufacture

 Carbon-based Monolith Support

a. b.
monolithic
structure

carbon

Carbon-coated monolith Integral-type carbon support

Catalysis and Catalysts - Manufacture

 (Co)Precipitation

Solution solution
wParameters
supersaturated solution –nature salts
–cA,cB,...
–T , pH
nucleation homogeneous or –ripening time
heterogeneous
–nucleation
promotors
growth –.......

Coprecipitation mixed oxides

Catalysis and Catalysts - Manufacture

Production of Catalysts by Precipitation
Mixed metal Sodium
nitrates tank carbonate tank

Filter
Mixed oxides
Drier and
and
calciner
carbonates
Mill

Precipitation
and ageing Powder mixing bin

Weighing
machines Catalyst pellets

Pelleting machine
Catalysis and Catalysts - Manufacture
 Coprecipitation

wPositive wNegative
–components well –difficult scale-up
mixed on an –at low loadings
atomic scale relatively low
–high loading dispersion
possible
–at high loadings
relatively high
dispersion
–high thermostability

Catalysis and Catalysts - Manufacture

 Structure of Coprecipitate in
Synthesis of Cu-Zn/Al2O3
brucite
layer

inter
layer

brucite
layer

inter
c0 layer

brucite
layer

inter
layer

brucite
layer

= metal ions (Cu2+, Zn2+, Al3+)

= hydroxyl ions

Catalysis and Catalysts - Manufacture = interlayer compounds (CO32-, H2O)

Catalysts Prepared by Coprecipitation
R e a c tio n
C a ta ly s ts
H y d ro g e n a tio n
S te a m re f o r m in g
M e th a n o l s y n th e s is
H ig h e r A lc o h o l S y n th e sCisu /C o /Z n /A l, C u /C o /Z n /C r
F is c h e r- T ro p s c h
S u p p o r ts f o r c a ta ly s ts
B a s ic s u p p o rt
C a ta ly tic e le m e n ts
N i/A l
N i/A l, N i/M g /A l
C u /Z n /A l, Z n /C r , C u /Z n /M g /A l
C o /C r, F e /A l
M g /A l

Catalysis and Catalysts - Manufacture

 Impregnation

wWetting of support with solution precursor

–"Wet" Excess solution
–"Dry" Amount of solution=Pore Volume
wDrying
–Critical, tendency towards "egg-shell" catalyst
wCalcination
–Critical
•bursting support
•interaction compounds
•sintering

Catalysis and Catalysts - Manufacture

 Catalyst Preparation by Impregnation
a. Bucket conveyor

Drip chute

Bucket
Wet impregnation Tipper

Drive wheel

To drying Bucket filter

Impregnating
solution
Impregnating basin

b. Impregnating
solution

Spray header
Dry impregnation
Support to be
impregnated

Catalysis and Catalysts - Manufacture

Rotating drum
 Relation between PZC and Surface Charge

Lower pH pH = PZC Higher pH

H H+ H H+ H H+ H H H
O- O- O-
O O O O O O
Si O Si O Si Si O Si O Si Si O Si O Si

pH pH < PZC pH = PZC pH > PZC

Surface Charge positive neutral negative

Species MOH2+ MOH MO-

Adsorption anions cations

PZC
Alumina 8-9
pH increase
Silica ~3
10% Alumina/Silica ~ 5
Catalysis and Catalysts - Manufacture
 Adsorption from [Pt(NH3)4]2+ solution

Adsorbed [Pt(NH3)4]2+ (mmol/g)

0.3

0.2 Silica gel

0.1

 -Alumina

6 7 8 9 10
pH

Catalysis and Catalysts - Manufacture

 Active-Phase Distributions

Uniform Egg-shell Egg-white Egg-Yolk

a b c d

Active phase Support

Catalysis and Catalysts - Manufacture

 Processes during Impregnation

Solution flow into pores adsorption

diffusion
Adsorption/desorption + diffusion adsorption

evaporation
Drying

Catalysis and Catalysts - Manufacture

 Impregnation of  -Alumina with Pt
4-
Cl Cl
OH Cl Pt Cl
2 Al + PtCl62- O O + 2 HCl
Al Al

Impregnation time increases

Active phase Support

Catalysis and Catalysts - Manufacture

 Impregnation of -Alumina with Pt
Influence of Coadsorbing Ions

a b c

Increasing citric acid concentration

Pt/Al2O3 Al2O3

Catalysis and Catalysts - Manufacture

 Impregnation of Monoliths with Ni
Influence of Drying Method

a. b. c. d. e.

Conventional Forced-flow Microwave Freeze drying

drying drying drying 1h 24 h

Catalysis and Catalysts - Manufacture

 Homogeneous Deposition Precipitation

wApplicable in precipitation upon increasing pH

–example: Ni2+ Ni(OH)2
wUpon heating (370 K) urea in water decomposes slowly:

CO(NH2)2 + 3 H2O CO2 + 2 NH4+ + 2 OH-

wpH increases slowly throughout particle

–homogeneous loading

Catalysis and Catalysts - Manufacture

 Homogeneous Deposition Precipitation

Peristaltic Pump (Gilson Minipuls)

Injection Speed 50 mL/h pH Electrode
pH

Time

2 g/L NaOH

SiO2 2g /2L
Ni(NO3)2.6H2O 0.5 g / 2 L

Catalysis and Catalysts - Manufacture

 Chemical Vapour Deposition

Catalysis and Catalysts - Manufacture

 Oil-Drop Coagulation

Sol
Distributor cone
Oil overflow to
recirculation

Organic phase

Oil

Water
Aqueous phase

Product to
ripening, washing,
and drying

Catalysis and Catalysts - Manufacture