KKEK3221 Chemical Engineering Reaction II

Introduction to catalyst, Types of catalyst, Characteristic of catalyst, Methods of characterizing catalyst, Methods of Manufacture of catalyst, Deactivation of catalyst 1.1 Introduction to Catalyst Catalysts have been used by mankind for over 2000 years (S.T.Oyama et al, 1986). Early uses of catalysts were in making of wine, cheese and bread. In US, the major uses are in petroleum refining and chemical production. A catalyst is a substance which accelerates the rate of reaction and is recovered unchanged in mass and chemical composition at the end of reaction. (Ostwald, 1894) - Catalyst provides alternative path i.e. lower energy barrier for reaction to occur. Non catalytic reaction: K = Ae-E/RT.(1) Catalytic reaction: Kc = Ae-Ec/RT...(2) => selectivities. - Catalyst can speed up reaction rate but cannot alter the equilibrium composition of the reaction. 1.2 Homogeneous and Heterogeneous catalyst Homogeneous catalyst: acids, bases, organo-metallic complexes Same phase as the reactants, normally separate from the products and recycled back into feed stream. e.g. acids, bases, organo-metallic complexes Kc>K as Ec<E - Small amount of catalyst can produce profound effect on rates or

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KKEK3221 Chemical Engineering Reaction II

Heterogeneous catalyst: different phase as reactants filtration to recover the solid powder, pellets packed in the reactor - e.g. solid powders, pellets, solid acid catalyst. 1.3 Structure of Heterogeneous Catalyst Many heterogeneous catalysts consists of ceramic or metallic material with irregular pores. Pore structure varies from catalyst to catalyst. (Fig.1.0. Pores of catalyst)

Fig.1. Pores in a catalyst. (Shaded area is solid material, unshaded area is the pores and the solid black areas represent clusters of active component attached to the walls of the pores) Generally the catalyst in a reactor is in the form of particles. The catalyst particles in a fluidized-bed or slurry reactor are relatively small diameter i.e. 1 100 m. The catalyst particles in fixed bed reactor are larger in diameter i.e. 110 mm. The fixed bed catalysts come in different shapes to accommodate different reactor designs and reaction characteristics.

1.3.1 Active components and Catalyst

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KKEK3221 Chemical Engineering Reaction II

The active component deposited near the geometrical external surface of the particle are known as eggshell catalyst. Those concentrated in the interior are known as egg yolk catalyst. 1.4. Characterization of Catalyst Structure i. Surface area - BET (Brunauer/Emmett/Teller) The internal surface area of a porous catalyst can be measured by adsorbing N2 onto the walls of the pores and determining the amount of N2 required for cover the surface exactly. i.e. Sp BET surface area. ii. Pore volume Vp (m3/g of catalyst) It can be determined by measuring the amount of a wetting liquid that is imbibed into the pores of the catalyst by capillarity i.e. the volume of liquid that is taken up by a known weight of catalyst. iii. Densities Particle density/ skeletal density/ bulk density - Particle Density, p weight of catalyst per unit geometric volume. E.g. perfectly spherical catalyst particle, with radius R. Geometric volume = 4R3/3 - Skeletal Density, s weight density of the solid material of which the catalyst particle is comprised. It can be measured by mercury displacement & helium displacement - Bulk Density, B weight of catalyst per unit geometric volume of reactor. Relationship: ( volume pores volume solids volume catalyst )+( )=( ) .(3) weight catalyst weight catalyst weight catalyst

V p+

1 1 = s p

or

Vp =

1 1 ...(4) p s

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KKEK3221 Chemical Engineering Reaction II

The porosity of the catalyst, is defined as: volume pores = V p P ..(5) geometric volume of catalyst particle

1.5 Methods of Manufacturing of Catalyst Precipitation Mixing of two or more solutions or suspensions of material and allow to precipitate. e.g. aqueous metal salt solution + aqueous alkali (ammonium hydroxide/carbonate) precipitation of an insoluble metal hydroxide/carbonate heating to form oxides

Followed by filtration, washing, drying, forming and heating. The final size and shape of catalyst particles are determined by forming process, which may also affect pore size and its distribution. Forming: pelletizing, extrusion, spheres, shell catalysts, granules After forming, the catalyst is activated (converted into active form through physical and chemical changes). Involves heating to cause calcination / decomposition, followed by reduction if a metallic catalyst is desired. Carried out continuously in a well-mixed vessel with careful control of pH. Advantages: More uniform mixing on a molecular scale of various catalyst ingredients. Distribution of active species through the final catalyst particle is uniform.

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KKEK3221 Chemical Engineering Reaction II

Ultimate sizes and shapes are not limited to the forms in which desired carriers are available. More control over pore size and pore size distribution.

For Example, magnesium oxide catalyst can be prepared by precipitating the magnesium from nitrate solution by adding sodium carbonate. The precipitate of magnesium carbonate is washed, dried and calcined to obtain the oxide.

Impregnation An active component is placed on a support that may be active / inactive. This method includes the following steps: Evacuation of the porous support Contacting the carrier with the impregnating solution Removing the excess solution Drying Calcination and activation For example, a nickel hydrogenation catalyst can be prepared on alumina by soaking the evacuated alumina particles with nickel nitrate solution, draining to remove the excess solution, and heating in an oven to decompose the nitrate to nickel oxide. Then, reduction of the oxide to metallic nickel is best carried out with the particles in the reactor by passing hydrogen through the equipment to prevent contamination with air and other gases which is poison.

1.6 Deactivation of Catalyst In designing catalytic reactors, it is required to assume the activity of the catalyst remains constant throughout the catalyst life. I.e. the total concentration of active sites, Ct accessible to the reaction does not change with time.

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KKEK3221 Chemical Engineering Reaction II

Problem- loss of catalytic activity as reaction takes place on catalyst. Types of Catalyst Deactivation: 1) Sintering (aging) (See et al, 1975) Loss of active surface area due to prolonged exposure to a highgas phase temperature. crystal agglomeration and growth of the metals deposited on the support narrowing / closing of the pores inside the catalyst pellet change in the surface structure due to

surface recrystallization formation / elimination of surface defects (active sites)

usually negligible at temperatures below 40% of the melting temperature of the solid e.g. Reforming of heptane over platinum on alumina

Figure 2: Pore closure. At high temperatures, the solid porous catalyst support becomes soft and flows, resulting in pore closure.

2) Fouling or Coking Reactions involving hydrocarbons i.e. coke deposited on the surface of a catalyst.

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KKEK3221 Chemical Engineering Reaction II

common to reactions involving hydrocarbons deposit of carbonaceous (coke) material on the surface of a catalyst can be reduced by running at elevated pressures (2000-3000 kPa) and hydrogen-rich streams catalysts deactivated by coking can be regenerated by burning off the carbon e.g. catalytic cracking of petroleum naphtha

Figure 3: Agglomeration of deposited metal sites. Atomic migration and agglomeration of small metal sites deposited on the surface into a larger site where the interior atoms are not accessible to the reaction.

3) Poisoning - Poisoning molecules become irreversibly chemisorbed to active sites. Thus reducing sites for main reaction. - The poisoning molecule: reactant and/or product, impurity in the feed stream. e.g. gasoline pump. Lead was used as an antiknock component in gasoline. Lead acts as an octane enhancer but it also poisoned the catalytic afterburner, which reduced NOx, CO and

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KKEK3221 Chemical Engineering Reaction II

hydrocarbons in the exhaust. Consequently, lead had to be removed from gasoline.

Assignment 1 Q1. Q2. Q3. Give an account on the importance of catalyst. Describe with flow diagram on one of the methods for manufacturing of catalyst. (i.e. Precipitation & impregnation). Assuming you are a catalyst specialist, how can the deactivation of catalyst be prevented or minimized?

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