Methods of Catalyst Preparation

U
T BH
II
Solid Heterogeneous Catalysts
@
CM

Bulk Catalysts Supported Catalysts

⫸ Precipitation/ Co precipitation ⫸ Impregnation
⫸ Sol Gel ⫸ Chemical Vapour Deposition
N

⫸ Hydrothermal (Solvothermal) ⫸ Ion Exchange

Dr. Nitai C. Maji 1
Bulk Preparation Steps in Catalyst Preparation
Bulk Catalyst Supported Catalyst

U
method
Phase I

Precipitation Support preparation using

BH
Co precipitation Sol-Gel Precipitation/ Sol-Gel

T
Phase II Impregnation

II
Aging
@ Washing
Phase III

Filtration/ Centrifugation/ Decantation

Drying
CM

Grinding/ Crushing
Phase IV

Calcination
Reduction
Dr. Nitai C. Maji 2
 Precipitation/ Co-precipitation Method

U
• The desired component is precipitated from the solution in Precipitation method

BH
• Co-precipitation is used for simultaneous precipitation of more than one
component

T
• In general, metal hydroxides are precipitated from their precursor salt solution due
to their low solubility

II
• Generally, Na+, K+, NH4+ hydroxides or bicarbonate are used as precipitating
agent
@
Al(NO3)3 + NH4OH → Al(OH)3 ↓ + NH4NO3
CM
N

Dr. Nitai C. Maji 3

 Steps in Precipitation

U
BH
1) Supersaturation

2) Nucleation

T
a. Homogeneous
b. Heterogeneous

II
1) Growth

2) Agglomeration @
CM
N

Dr. Nitai C. Maji 4

 Sol-Gel Method

U
• Initially a stable colloidal solution called SOL is formed

BH
• It can be obtained by hydrolysis and partial condensation of precursors such as an
inorganic salt or a metal alkoxide
• The further condensation of sol particles into a three dimensional network produces

T
a GEL

II
• When gels are dried by evaporation, the dried product is called XEROGEL
• When the gels are dried by supercritical drying, the dried gel is called AEROGELS.
@
The aerogel retains high porosity and has very high pore volume.
CM
N

Dr. Nitai C. Maji 5

 General scheme of preparation by Sol-Gel

U
T BH
II
@
CM
N

Dr. Nitai C. Maji 6

 Impregnation Method
Impregnation is a technique in which a solution of the precursor of the active phase

U
is brought in contact with the support

BH
Solution of metal precursor Support

T
II
Dry/Incipient Impregnation Wet Impregnation
(Vsolvent ≈ Vpores)
@ (Vsolvent >> Vpores)
CM

Drying
N

Dr. Nitai C. Maji

Thermal Treatment 7
 Incipient Impregnation

U
Determine the porosity of the support to the solvent (typically water) so that the
pores are just filled i.e. the support appears to be just moistened by the solvent

BH
Prepare a solution of a suitable salt in water so that the concentration of the salt

T
gives the desired loading of the additive when the pores are totally filled

II
The prepared solution is contacted with the support so that pores are totally filled
@
Dry the material (120 °C, 16h)
CM

Calcine the material (550 °C)

N

Dr. Nitai C. Maji 8

 Impregnation: Advantages and Disadvantages

U
Incipient:

BH
• The incipient involves a pore filling technique and is suitable for low
loadings of additives.

T
• It is a very facile method and requires very less time.

II
• However, it can be difficult to control and can give non-uniform deposition
@
of the impregnated material on the support.

Wet:
CM

• Wet impregnation technique is used for high loading of metals

• It is easy to prepare a uniform layer of active matter on the catalyst’s surface
N

Dr. Nitai C. Maji 9

 Calcination

U
• Thermal treatment in limited oxidizing atmosphere

BH
• Temperature is usually slightly higher than that of the catalyst
operating temperature

T
• Thermally unstable compounds (carbonates, hydroxides) decompose

II
and are converted to oxides

• New compounds may be formed, if thermal treatment is carried out at

higher temperatures@
• Physical and mechanical properties and pore structures can also
CM

change.
N

Dr. Nitai C. Maji 10

 Effect of Calcination

U
T BH
II
@
CM
N

Dr. Nitai C. Maji 11

 Promoters and Inhibitors

U
• Promoters are generally defined as substances added during preparation

BH
of catalysts

• It improves the activity or selectivity or stabilize the catalytic agents

T
• Addition of small quantities of alumina to an iron catalyst employed in

II
ammonia synthesis prevents sintering of the iron crystallites

@
• Inhibitors act opposite to promoters

• It can reduce catalyst activity, selectivity or stability

CM

• It is particularly useful for reducing the activity of a catalyst for

undesirable side reactions

• In oxidation of ethylene, ethylene dichloride is added to inhibit CO2

N

formation
Dr. Nitai C. Maji 12
 Catalyst characterization

U
Determination of its physical and chemical characteristics (responsible for its
performance in a reaction)

BH
• Surface area and porosity ( micro, meso and macro)
• Bulk solid structure, phase composition, crystallite size

T
• Surface chemical properties such as:

II
o Location and oxidation state of active metals
o Acid-base property
o Reducible–oxidizable property
@
• Surface morphology
• Aggregate properties such as aggregate or particle size
CM

• Catalytic properties : activity , selectivity, stability

N

Dr. Nitai C. Maji 13

 Different catalyzation methods

U
BET

BH
BJH
Structural
Analysis TGA/DTA
XRD
TPR

T
TPD
Thermal

II
analysis
FTIR

XPS
Characterization
methods
@ Spectroscopic
Raman
techniques
SEM
CM

Optical
TEM

Electron
Microscopic
techniques
N

Chemisorption
techniques
Dr. Nitai C. Maji 14
 Structural Analysis

U
(a) Surface area
• BET ( Brunauer, Emmet and Teller) method used for analyzing

BH
multilayer physisorption isotherms of inert gases to determine the surface area

(b) Pore analysis

• BJH method

T
(c) X-Ray Diffraction (XRD)

II
• Can detect crystalline materials having crystal domains greater than 3-5 nm.
• Characterization of bulk crystal structure and chemical phase composition.

@
CM
N

BET: Isotherm
Dr. Nitai C. Maji
X-Ray Diffractogram 15
 Electron Microscopy
TEM SEM

U
T BH
II
@
CM
N

• determines the micro texture and structures • Image the topography of solid surface
• Resolution better than 0.2 nm • Resolution better than 5 nm
Dr. Nitai C. Maji 16
 Chemisorption

U
Active metals are deposited on the surface of the support: Pt/Al2O3, Pt/C, Ni/Al2O3
etc.

BH
Only a fraction of the total deposited metal is actually exposed to the incoming
reactant molecules for participation in a reaction.

T
Chemisorption is mainly used to study :
(1) metal dispersion and

II
(2) active metal area

The sample is exposed to a gas (H2 and CO) that can chemisorb on the active metal.
@
At monolayer coverage, the average number of surface metal atoms associated with
adsorption of each gas molecule is determined.
CM

NS
Dispersion (D) of metal =
NT

NS = Number of exposed surface atoms

N

NT = Total number of metal atoms present in the sample

Dr. Nitai C. Maji 17
 Thermal Analysis

U
(a) Temperature programmed reduction (TPR)
• It measures the rate of reduction of active metals as function of temperature.

BH
• It can be correlated with activity of catalysts

(b) Temperature programmed desorption (TPD)

T
• Measurement of rate of desorption of adsorbed molecules as function of temperature
• Mainly used to of study acid –base property of catalysts

II
(c) Thermo Gravimetric Analysis (TGA)
@
• Measurement of weight loss (or gain) as a function of temperature in a controlled
gaseous atmosphere
• Process associated with mass change can be detected and analyzed
CM

(d) Differential Thermal Analysis (DTA)

• Monitoring the temperature difference between sample and reference
• Process associated with latent heat of transition can be detected and analyzed
N

Dr. Nitai C. Maji 18