CRE II Heterogeneous Catalysis L4

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

Chemical Kinetics
Collision Theory Collisions between reacting molecules are necessary before a reaction can occur.

Only those collisions having sufficient energy

are effective in bringing about a reaction activation energy. Colliding molecules must be properly oriented with respect to one another for the reaction to take place.
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Steps of Catalytic Reactions

Every catalytic reaction is a sequence of elementary

steps, in which reactant molecules bind to the catalyst,

where they react, after which the product detaches

from the catalyst, liberating the latter for the next cycle. 3

Factors affecting reaction rate: Concentrations of reactants Catalyst Temperature Surface area of solid reactants or catalyst
Surface Area

Turnover frequencies, Rates and numbers

CATALYSIS IS A KINETIC PHENOMENON Sequence of elementary steps at steady state: diffusion (bulk, film, surface) - adsorption-reactiondesorption- diffusion TOF= number of product molecules formed per unit area per sec(molecules.cm-2.sec-1) Or, TOF= number of product molecules formed per active site per sec(molecules.sec-1) only if active site is known.
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TOT= 1/TOF = turnover time, time necessary to form a product molecule(sec); TOR = Turnover rate = TOF X Surface area
TON= TOF X total reaction time;

Conversions, Rates and Rate constants

Conversion = % Reactant converted;

Reaction rate = kp X f(Pi) or kc X f(Ci)

k = A exp(-E#/RT); A is temp independent.

TOFs between 0.0001 and 100 in industry; Temp

adjusted to get the desired rates. E# ~ 35-45 Kcal/mol for isom, cyclisation, cracking, dehydo / hydrogenolysis; HighT needed. E# ~ 6-12 Kcal/mol for hydrogenation;
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Selectivity
The selectivity (Sp) of a reaction is the fraction of the starting material that is converted to the desired product P. It is expressed by the ratio of the amount of desired product to the reacted quantity of a reaction A . In addition to the desired reaction, parallel and sequential reactions can also occur.

np vp Sp= nA,o - nA vA =

np vA

nA,o - nA vp

mol/mol or %

Stability
The chemical, thermal, and mechanical stability of a catalyst determines its lifetime in industrial

reactors.
Catalyst stability is influenced by decomposition,

coking, and poisoning. Catalyst deactivation can

be followed by measuring activity or selectivity as a function of time.

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Presently the efficient use of raw materials and

energy is of major importance, and it is prefer-able to optimize existing processes than to develop new ones. For various reasons, the target quantities should be given the following order of priority: Selectivity >Stability> Activity

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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 and mass index. The E factor :Ratio of Waste [kg] to Product[kg]), is an output orientated indicator, whereas the Mass index (Ratio of all Raw materials [kg] to the Product [kg]) is an input oriented indicator.
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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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Solid Catalysts
Catalyst composition
-Active phase Where the reaction occurs (mostly metal/metal oxide) -Promoter Textual promoter (e.g. Al - Fe for NH3 production)
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Catalyst

Support

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

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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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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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