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CRE II Heterogeneous Catalysis

L6

Prof. K.K.Pant Department of Chemical Engineering

IIT Delhi.

CRE II Heterogeneous Catalysis L6 Prof. K.K.Pant Department of Chemical Engineering IIT Delhi. <a href=kkpant@chemical.iitd.ac.in " id="pdf-obj-0-12" src="pdf-obj-0-12.jpg">

Comparison between Homogeneous

and heterogeneous catalysts

3
Active site pore porous solid
Active site
pore
porous
solid

Activity: of a catalyst depends on the texture and electronic structure. Activity of a catalyst can be explained by:

Active centers on the surface of the catalyst

Geometry of surface Electronic structure Formation of surface intermediates

Efficiency : of a catalyst depends on Activity, Selectivity and Life.

Inhibitor: substances added to the catalyst during its manufacture to reduce its activity.

Coking/Fouling: deposition of carbonaceous material on the surface of the catalyst -

Common to reactions involving

hydrocarbons

Catalyst preparation

Three fundamental stages of catalyst preparation may be distinguished:

Preparation of the primary solid (or first precursory

solid) associating

all

the

useful

components

(e.g.,impregnation or co-precipitation, or in the case of

zeolites, crystallization);

Processing of that primary solid to obtain the catalyst precursor, for example by heat treatment;

Main routes (Catalyst Preparation)

deposition, Impregnation Precipitation, co-precipitation, gel formation.

Solid Catalysts

Solid Catalysts precursor solution Support add acid/base with pH control precipitate or deposit precipitation filter &

precursor

solution

Support

add acid/base
add acid/base
Solid Catalysts precursor solution Support add acid/base with pH control precipitate or deposit precipitation filter &

with pH control

precipitate

or deposit

precipitation

filter & wash the resulting precipitate

Support

Solid Catalysts precursor solution Support add acid/base with pH control precipitate or deposit precipitation filter &
Solid Catalysts precursor solution Support add acid/base with pH control precipitate or deposit precipitation filter &
Concentration Amount adsorbed
Concentration
Amount
adsorbed
Solid Catalysts precursor solution Support add acid/base with pH control precipitate or deposit precipitation filter &
Drying

Drying

& firing

 

Drying

& firing

& firing

Impregnation Method

Impregnated catalysts have many advantages compared to precipitated catalysts. Their pore structure and specific surface area are largely determined by the support.

Since support materials are available in all desired ranges of surface area, porosity, shape, size, and

mechanical stability, impregnated catalysts can be

tailor-made with respect to mass transport

properties.

o Impregnation

Fill the pores of support with a metal salt solution of sufficient concentration to give the correct loading.

Dry mixing

Physically mixed, grind, and fired.

Principle of catalyst preparation by incipient wetness impregnation 12

Principle of catalyst preparation by incipient wetness impregnation

Deposition (Impregnation)

Impregnation consists in contacting a solid with a liquid containing the components to be deposited on the surface. During impregnation different processes take place with different rates:

* selective adsorption of species (charged or not) by coulomb force, Vander Waals forces or H-bonds; * ion exchange between the charged surface and

the electrolyte;

Catalysts- Preparation process

Addition of support

Metal salts

Catalysts- Preparation process Addition of support Metal salts Co-precipitation Filtration Drying Activation Final Catalyst
Catalysts- Preparation process Addition of support Metal salts Co-precipitation Filtration Drying Activation Final Catalyst

Co-precipitation

Catalysts- Preparation process Addition of support Metal salts Co-precipitation Filtration Drying Activation Final Catalyst
Catalysts- Preparation process Addition of support Metal salts Co-precipitation Filtration Drying Activation Final Catalyst

Filtration

Drying
Drying
Filtration Drying Activation

Activation

Filtration Drying Activation

Final Catalyst

Catalysts- Preparation process Addition of support Metal salts Co-precipitation Filtration Drying Activation Final Catalyst

Impregnation : by filling the pores of a preformed support with metal salt solution.

Wet Impregnation : Here volume of the solution is substantially larger than the pore volume of the support.

Incipient wetness : Amount of the solution added is equal to or slightly less than the pore volume of the support.

Ion Exchange Method: Requires some functionalisation of the support and exchanging the functional species with the species to be loaded.

Catalyst preparation

All experimental parameters are critical for

determining the characteristics of the solid obtained

after the first step:

* aggregate morphology of the carrier used, if any; * quantities used (solutions, carrier); * concentrations; * stirring conditions (shape and volume of vessel

are important);

* temperature and temperature changes; * sequence and duration of all options;

BET S.A.

BET S.A. m 2 /g

Solid Catalysts

Preparation of catalysts

Catalysts need to be calcined (fired) in order to decompose the precursor and to received desired thermal stability. The effects of calcination temperature and time are shown in the figures.

100

75

50

75 50
75 50
 

25

0

 

500

600

700

800

900

Temperature °C

40

0

BET S.A. BET S.A. m /g Solid Catalysts • Preparation of catalysts – Catalysts need to
BET S.A. BET S.A. m /g Solid Catalysts • Preparation of catalysts – Catalysts need to

0

10

Time / hours

Precipitation Method: Catalysts are precipitated from aqueous solutions e,g. Water. Hydrolysis depends on pH, T and concentration of the salt etc.

Governed by solubility of product and proceeds with the formation of the nuclei and their growth.

Metal salt(nitrate, chloride, sulfate, oxalate) +NH 3 or Na (Urea, hydroxide and carbonate) +support = metal hydroxide/carbonate on

support