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CRE II Heterogeneous Catalysis

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

-Catalyst
Allow reactions occur under a milder conditions, e.g. at lower temperatures for those heat sensitive materials

It is important to remember that the use of catalyst DOES NOT vary DG & Keq values of the reaction concerned, it merely change the PACE of the process.

Whether a reaction can proceed or not and to what extent a reaction can proceed is solely determined by the reaction thermodynamics, which is governed by the values of DG & Keq, NOT by the presence of catalysts. The reaction thermodynamics provide the driving force for a rxn; the presence of catalysts changes the way how driving force acts on that process.

e.g CH4(g) + CO2(g) = 2CO(g) + 2H2(g) DG373=151 kJ/mol (100 C) & DG973

=-16 kJ/mol (700 C)


=>At 100C, DG373=151 kJ/mol > 0.

There is no thermodynamic driving force, the reaction wont proceed with or without a catalyst

At 700C, DG373= -16 kJ/mol < 0. The thermodynamic driving force is there. However, simply putting CH4 and CO2 together in a reactor does not mean they will react. Without a proper catalyst heating the mixture in reactor results no conversion of CH4 and CO2 at all.

When Pt/ZrO2 or Ni/Al2O3 is present in the


reactor at the same temperature, equilibrium conversion can be achieved (<100%).
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Why R& D in catalysis is important?


90 % of chemical industry involve products made using catalysts (food, fuels, polymers, textiles, pharma/

agrochemicals,etc)
For discovery/use of alternate sources of

energy/fuels/ raw material for chemical


industry.

For Pollution control-Global warming. For preparation of new materials (organic &

inorganic-eg: Carbon Nanotubes).

Catalysis is multidisciplinary ( physics, chemistry, Material science (nanomaterial) & chem. Engg. )
The catalyst is an inorganic solid; Catalysis is a surface phenomenon; solid state and surface structures play important roles. Adsorption, desorption and reaction are subject to thermodynamic, transport and kinetic controls

(chem engg);

Adsorbate-substrate and adsorbate adsorbate interactions are both electrostatic and chemical (physical chemistry). The chemical reaction is organic chemistry.

Concept of Green catalysis


Technology is called Green if it uses raw
materials efficiently, such that the use of toxic and hazardous reagents and

solvents can be avoided while formation of waste or undesirable by-products is

minimized.

Concept of Green catalysis

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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 360 392

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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There is a substantial increase in E factors on going downstream from bulk chemicals (<15) to fine chemicals (5 >50) and specialties (25 >100).

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Action of Catalysts
Catalysis action - Reaction kinetics and mechanism Catalyst action leads to the rate of a reaction to change. This is realised by changing the course of reaction (compared to non-catalytic reaction)

Forming complex with reactants/ products, controlling the rate of elementary steps in the process.
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For comparative measurements, such as catalyst screening, determination of process para-meters, optimization of catalyst production conditions, and deactivation studies, the following activity measures can be used: Conversion under constant reaction conditions Space velocity for a given, constant conversion Spacetime yield Temperature required for a given conversion
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Catalysts are often investigated in continuously operated test reactors, in which the conversions attained at constant space velocity are compared . The space velocity: is the volume flow rate V0, relative to the catalyst mass mcat: (V0/mcat) (made under constant conditions of starting material ratio, temperature, and pressure).
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Often the performance of a reactor is given relative to the catalyst mass or volume, so that reactors of different size or construction can be compared with one another. This quantity is known as the spacetime yield STY STY= Desired product quantity/ Catalyst vol. time

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Comparison of catalyst activities


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Mode of Action of Catalysts


The suitability of a catalyst for an industrial process depends mainly on the following three properties: Activity Selectivity Stability (deactivation behavior) The question which of these functions is the most important is generally difficult to answer because the demands made on the catalyst are different for each process.
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Activity
Activity is a measure of how fast one or more reactions proceed in the presence of the catalyst. Activity can be defined in terms of kinetics or from a more practically

oriented viewpoint.
In a formal kinetic treatment, it is appropriate to measure reaction rates in the temperature and concentration ranges that will be present in the reactor.

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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.
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Potential energy diagram of a heterogeneous catalytic reaction

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

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Turnover frequencies, Rates and numbers


CATALYSIS IS A KINETIC PHENOMENON Sequence of elementary steps at steady state: diffusion (bulk, film, surface) - adsorptionreaction-desorption- diffusion TOF= number of product molecules formed per unit area per sec(molecules.cm-2.sec-1) 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;


TON must be >100 to be industrially useful.

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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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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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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.

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np vp Sp= nA,o - nA vA =

np vA

nA,o - nA vp

mol/mol or %

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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 preferable 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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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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