Hình dạng của một số xúc tác công nghiệp

(Shapes of Industrial Catalysts)

Irregular granule Sphere Pellet Extruded

cylindrical

Ring Minilith Wagon wheel Trilobe

Monolith Monolith Foam

ceramic metallic

Catalysis and Catalysts - Manufacture

 Sự so sánh các tính chất-ứng dụng giữa các dạng
xúc tác - 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

Specific Surface Area, SA (m2/g)

Crystalline Size, d (nm)

Catalysis and Catalysts - Manufacture

 Ví dụ về cách sản xuất xúc tác (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

 Chuẩn bị xúc tác (Catalyst Preparation)
 Bulk catalysts (xúc tác khối)
 Supported catalysts (xúc tác mang)
– Supports
• Silica
• Alumina
• Zeolites
• Activated Carbon
– Attachment of active phase (Pha hoạt tính được đưa lên giá mang)
• Co-precipitation
• Impregnation
• Deposition-precipitation
• Chemical vapour deposition (CVD)
• Sol-gel method

Catalysis and Catalysts - Manufacture

 Giá mang xúc tác (Catalyst Supports)
 Function
– carrier active phase
– stabilizes active phase
– access to active sites
Catalysis and Catalysts - Manufacture
 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
Catalysis and Catalysts - Manufacture
 Giá mang xúc tác và ứng dụng
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

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

 Sản xuất Silaca xốp
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-

S iO 4 4 - S i3 O 1 0 8 - S i2 O 7 6 -

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
-
OSi OS -
i O S
i4
O 8-
1
2
O O F
our
-rin
g
-
OSi OS -
i 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
HO Si OH O 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

Mixing
Washing

Drying
Washing
Drying

Milling

Classifi-
cation Classification Milling

Packaging
Packaging

Catalysis and Catalysts - Manufacture

 Sản xuất Al2O3 xốp
Production of Alumina (Porous Al2O3)
Al is amphoteric (lưỡng tính)

low pH, soluble high pH, soluble

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

base acid

precipitate precipitate

Catalysis and Catalysts - Manufacture

 Vùng kết tủa của các hợp chất Alumin
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

plus amorphous material

pseudo boehmite

Crystallised
hydrargillite
Poorly crystallised

Crystallized bayerite
Several precipitates,
dependent on conditions

Catalysis and Catalysts - Manufacture

 Các dạng thù hình khác nhau của Alumina
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 -Al2O3 -Al2O3 -Al2O3
spinel structure: cubic close packing
Heating at about 1170 - 1270 K

-Al2O3 -Al2O3 -Al2O3

Heating above 1370 K

-Al2O3
Catalysis and Catalysts - Manufacture
 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

Catalysis and Catalysts - Manufacture

 Pore Volume Distributions
0.10
0.5

0.08
0.4
Wide-pore Silia -Alumina
dV /dd (ml/g/nm)

dV /dd (m l/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
-Alumina ZSM-5
0.008 8

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

0.006 6

0.004 4

2
0.002

0
0.000
0.0 0.5 1.0 1.5 2.0
1 10 100 1000 d pore (nm)
Catalysis and Catalysts - Manufactured pore (nm)
 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 Diameters of Molecules
Compared with Zeolite Pore Size

1
K in etic d iam e ter [n m ]

Zeolite-X, Y
Kinetic diameter (nm)

0.8

0.6 ZSM-5

0.4 Zeolite-4A

0.2

Catalysis and Catalysts - Manufacture

 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 RE3+ 1st
solution Exchange

Filtration &
Na+
washing
solution

Heating

NH4+ or RE3+ 2nd

Na+
solution Exchange
solution

Filtration &
washing

Final drying
Catalysis and Catalysts - Manufacture
 Zeolites Classified by their Si/Al Ratio

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

 Activated Carbons

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

Catalysis and Catalysts - Manufacture

 Activated Carbon

Carbonaceous material peat, coal, biomass, sugar,

polymers
High T
Pyrolysis ( nhiệt phân)

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

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
 Parameters
supersaturated solution – nature salts
– cA,cB,...
homogeneous or – T , pH
nucleation heterogeneous – ripening time
– 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 carbonates
calciner

Mill

Precipitation
and ageing Powder mixing bin

Weighing
machines Catalyst pellets

Catalysis and Catalysts - Manufacture

Pelleting machine
 Coprecipitation

 Positive  Negative
– components well mixed – difficult scale-up
on an atomic scale – at low loadings relatively
– high loading possible low dispersion
– 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

Catalysis and Catalysts - Manufacture

 Impregnation

 Wetting of support with solution precursor

– "Wet" Excess solution
– "Dry" Amount of solution=Pore Volume
 Drying
– tendency towards "egg-shell" catalyst
 Calcination
• 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 = P ZC 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
Silica gel

0.2

0.1
-Alumina

0
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/Al 2O 3 Al 2 O 3

Catalysis and Catalysts - Manufacture

 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

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