CRE II Heterogeneous Catalysis L7

Prof. K.K.Pant Department of Chemical Engineering IIT Delhi. kkpant@chemical.iitd.ac.in

Catalysts- Preparation process

Metal salts

Addition of support

Co-precipitation

Filtration

Drying

Activation

Final Catalyst

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;

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;

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

6

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.
7

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.
40 100 75

BET S.A. m2/g

50
25 0 500 600 700 800 900

BET S.A.

0 0

Time / hours

10

Temperature C
8

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) +NH3 or Na (Urea, hydroxide and carbonate) +support = metal hydroxide/carbonate on support
9

ACID CATALYSIS
SOLID ACID CATALYSTS Examples: Zeolites SAPOs Clays; pillared clays Ion-exchange resins Oxides; X, SO4-oxides Mixed oxides; amorphous Heteropoly acids Two types of acid sites are recognized - Brnsted - Lewis

Catalytic cracking is the Largest user of any solid Catalyst.

Mineral acids such as H2SO4, HF and AlCl3 are widely used in the industry.
The US petroleum refining industry alone uses ~ 2.5 M tons of H2SO4 and ~ 5000 tons of an hydrous HF annually

12

Reactions / processes based on acid catalysis

Name of reaction Description Solid-acid catalyst used Silica-alumina; ZeoliteY ZSM-5 Cracking / Crack large molecules in hydrocrac petroleum oils king FCC additives for more C3 and octane Dewaxing Crak n-paraffins (waxes) in petroleum oils IsodeIsomerization of waxy waxing molecules. Xylene p- and o-xylenes from misomerixylene. sation

ZSM-5 SAPO-11 ZSM-5; Mordenite

Reactions / processes based on acid catalysis

Name of reaction Naphtha reforming Hydrotreating Hydration Description Solid-acid catalyst used

Isomerization reactions for aromatization of paraffins.

Remove N and S from petroleum oils Hydrate olefins to alcohols.

Chlorided alumina
Alumina support

Ion-exchange resin; ZSM-5; Heteropolyacids

Pore Size and Shape

Pore Diameter micropores (< 2 nm) mesopores (2 50 nm) macropores (> 50 nm) Pore Shape cylinder slit ink-bottle wedge

How do molecules bond to surfaces?

Two principle modes of adsorption of molecules to surfaces.

-Physical

Adsorption:

The only bonding is by weak van der waals-type

forces. There is no significant redistribution of electron density in either the molecule or at the substrate surfaces.
16

Terminology
Substrate- Frequently used to describe the solid surface onto which adsorption can occur; the substrate is also occasionally (although not here) referred to as the adsorbent. Adsorbate- The general term for the atomic or Molecular species which are adsorbed (or are capable of being adsorbed) onto the substrate. Adsorption- The process in which a molecule becomes adsorbed onto a surface of another Phase. (different from Absorption which is used when describing uptake into the bulk of a solid 17 or liquid phase )

Adsorptive

Gas to be adsorbed

Adsorbent
Adsorbate Micropore Mesopore Macropore

Material on which gas adsorbs

Adsorbed gas Pore width 2 nm Pore width 250 nm Pore width 50 nm