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CRE II Heterogeneous Catalysis

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

Basic concept of green catalysis


1. Indicators to measure the efficiency and environmental impact of a reaction. Atom Efficiency: is the molecular weight of the desired product divided by the total

molecular weight of All Products.

Concept of Atom efficiency & E -Factor


Atom efficiency =
The molecular weight of the desired product The total weight of all products.

Another useful indicator of environmental acceptability is the E factor- the weight of waste or undesirable by product by the Weight of the desired product.

E factor:
Mass balances of alternative routes in

chemical processing can be compared


using measures E factor .

The E factor :Ratio of Waste [kg] to


Product[kg]), is an output orientated

indicator.

For example the conventional oxidation of a secondary alcohol 3C6H5CHOHCH3 + 2Cr2O3 + 3H2SO4
3C6H5COCH3 + Cr2(SO4)3 + 6H2O 396 120

Atom efficiency of 360/860 = 42%.


C6H5CHOHCH3 + 1/2O2

C6H5COCH3 + H2O Atom efficiency of 120/138 = 87%, with water as the only by product.
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Active site: is a point on the catalyst surface that can form strong chemical bonds with an adsorbed atom/molecule. These sites are unsaturated atoms in the solid resulting from: Surface irregularities

Dislocations
Edges of crystals

Cracks along grain boundaries

Solid Catalysts
Some common solid support / carrier materials Alumina Inexpensive Surface area: 1 ~ 700 m2/g Acidic Silica Inexpensive Surface area: 100 ~ 800 m2/g Acidic
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Catalysis in the Chemical Industry


Hydrogen Industry (coal, NH3, methanol, FT,

hydrogenations / HDT, fuel cell).


Natural gas processing (SR,ATR,WGS,POX)

Petroleum

refining

(FCC,

Hydrotreating,

Hydrocracking, Reforming, Alkylation etc. etc.) Petrochemicals(monomers, bulk chemicals).


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Fine Chem.(pharma, agrochem, fragrance, textile, coating, surfactants,laundry etc)

Environmental Catalysis (auto exhaust,


deNOx, )

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Types of Catalysts & Catalytic Reactions


The types of catalysts Classification based on the its physical state, a catalyst can be gas liquid

solid
Classification based on the substances from which a catalyst is made
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Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)


Organic (organic acids, enzymes etc.)

Types of catalysts
Classification based on the ways catalysts work

Homogeneous - both catalyst and all reactants/products are in the same phase (gas or liq) Heterogeneous - reaction system involves multi-phase (catalysts + reactants/products)
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Classification of Catalysts

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Comparison between Homogeneous and heterogeneous catalysts

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Active site

porous solid

pore

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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.

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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

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Solid Catalysts
Some common solid support / carrier materials Alumina Inexpensive Surface area: 1 ~ 700 m2/g Acidic Silica Inexpensive Surface area: 100 ~ 800 m2/g Acidic
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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;

Activation of the precursor to give the active catalyst: reduction to metal (hydrogenation catalysts), formation of sulfides (hydrodesulphurization), deammoniation (acidic zeolites). Activation may take place spontaneously at the beginning of the catalytic reaction (selective oxidation catalysts).
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Main routes (Catalyst Preparation)

deposition,
Impregnation

Precipitation,
co-precipitation,

gel formation.

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Solid Catalysts
Support

Drying & firing


precursor solution add acid/base filter & wash with pH control precipitate or deposit the resulting precipitation precipitate

Support

Amount adsorbed

Drying & firing

Concentration
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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.
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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.

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Principle of catalyst preparation by incipient wetness impregnation


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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


Metal salts

Addition of support

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.
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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;

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

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25 0 500 600 700 800 900

BET S.A.

0 0

Time / hours

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Temperature C
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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
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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

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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 SYSTEM The pore system of a support is usually irregular in shape and contains macropores due to the spaces between individual crystallites, with diameters of the order of 100 nm, and micropores with characteristic dimensions of 510 nm. A good support offers (1) Controlled surface area and porosity, (2) Thermal stability, (3) High mechanical strength against crushing and attrition.
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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.
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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 41 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

Coverage- A measure of the extent of adsorption of a species onto a surface. Exposure- A measure of the amount of gas which as surface has seen; more specifically it is the product of the pressure and time of

exposure.
(normal unit is the langmuir ,where 1 L=10-6 Torr *s).

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Chemisorption: A chemical bond involving substantial rearrangement of electron density, is formed between the adsorbate and substrate. The Nature of this bond may lie anywhere between the extremes of virtually complete ionic or complete covalent character.
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Chemisorption: There is some sort of interaction between the surface of the catalyst and the reactant molecules which makes them more reactive. This might involve an actual reaction with the surface, or some weakening of the bonds in the attached molecules.

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Bonding strength between H2 & metal surface increases with increase in vacant d orbital.

Maximum catalytic activity will not be realized


if the bonding is too strong and the products

are not easily desorbed from the surface.

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Most active Metals: Co, Ni, Rh, Ru, Os,Pd, Ir, Pt, Approximately one vacant d orbital per atom.
Whereas, V, Cr, Mo, W etc. each metal has a large number of vacant d orbital and are less active as a result of strong adsorption for the reactants or products or both. However oxides of Mo (MoO2) and Cr (Cr2O3) are quite active for most rexns involving H2.
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The Chemical reaction happens.


At this stage, both of the reactant molecules might be attached to the surface, or one might be attached and hit by the other one moving freely in the gas or liquid. The product molecules are desorbed. Desorption means that the product molecules break away. This leaves the active site available for a new set of

molecules to attach to and react.

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Physical Adsorption Vs. Chemisorption


Item Forces of attraction Specificity Quantity Heat Effects Activation energy Effect of Temp. Physical Adsorption Weak VanderWaals forces Low Large Exothermic, 1-15 kCal/mol Low Rapid at low temperatures & reach equilibrium quickly. Beyond TC of the gas, no ads. Increases with increase in pressure Chemisorption Strong valency forces High Small Exothermic, 10-100 kCal/mol High Slow at low temp., Rate increases with temp.

Effect of Pressure

Little effect

Surface Layers

Whole surface active Multi-layer adsorption

Fraction of surface only Mono-layer adsorption


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Physical Adsorption
Texture and morphology specific surface area of catalyst pore size pore shape pore-size distribution (same size or various sizes?) pore volume

Chemisorption
Surface Characterization Specific surface area of phases Types of active sites Number of active sites Reactivity of active sites Stability of active sites

Chemisorption
Metal Dispersion

Supported Metal Particles

Adsorption at gas/solid interface.


Adsorption: Term used to describe the process Whereby a molecule(the adsorbate) forms a Bond to a solid surface(an adsorbent). Fractional surface coverage Ns number of sites occupied by adsorbate = N total number of adsorption sites When =1,NS=N and an adsorbed monolayer is formed.The fractional coverage depends on pressure of adsorbing gas phase species. This =(P) relationship is called an adsorption isotherm.
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Langmuir Adsorption Isotherm


Simple approach to quantitatively describe an adsorption process at the gas/solid interface

N = N +N number of vacant sites V S


Assumptions:

Solids surface is homogeneous and contain a number of equivalent sites,each of which is occupied by a single adsorbate molecule.
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A dynamic equilibrium exist between gas phase reactant and adsorbed species. No interactions between adsorbed species. Adsorbed species localised, Hads is independent of coverage ..

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