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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
indicator.
For example the conventional oxidation of a secondary alcohol 3C6H5CHOHCH3 + 2Cr2O3 + 3H2SO4
3C6H5COCH3 + Cr2(SO4)3 + 6H2O 396 120
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
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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Petroleum
refining
(FCC,
Hydrotreating,
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solid
Classification based on the substances from which a catalyst is made
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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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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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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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deposition,
Impregnation
Precipitation,
co-precipitation,
gel formation.
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Solid Catalysts
Support
Support
Amount adsorbed
Concentration
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Impregnation Method
Impregnated catalysts have many advantages
o Impregnation
Fill the pores of support with a metal salt solution of sufficient concentration to give the correct loading.
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Deposition (Impregnation)
Impregnation consists in contacting a solid with a
liquid containing the components to be
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
50
25 0 500 600 700 800 900
BET S.A.
0 0
Time / hours
10
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
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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Chlorided alumina
Alumina support
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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-Physical
Adsorption:
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
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.
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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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Effect of Pressure
Little effect
Surface Layers
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
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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