Catalyst Synthesis Methods

Prepared By

Pratik Shah 07BCH036

Guided By Prof. Femina J. Patel

Contents
What is a CATALYST ? Types of catalysts Properties of catalysts Characteristics of catalysts Catalyst materials Catalyst characterization techniques Catalyst synthesis techniques
Sol Gel Method Combustion Synthesis Ion-exchange Wet Impregnation Co-precipitation Adsorption Citric Acid

What is a CATALYST ?
A catalyst, is a material that enhances the rate and selectivity of a chemical reaction and in the process is cyclically regenerated.
A catalyst is a substance that alters the rate of a reaction by providing an alternate path of lower activation energy. Since catalysts are not consumed in a reaction, very small quantities of catalyst are required to enhance a reaction rate. A catalyst is any substance that alters the rate of a reaction without itself being consumed.

Types of Catalysts
Heterogeneous catalysis Homogeneous catalysis Homoheterogenized catalysis Biocatalysis

Heterogeneous Catalysts
Heterogeneous catalysts are those which act in a different phase than the reactants. Most heterogeneous catalysts are solids that act on substrates in a liquid or gaseous reaction mixture. The total surface area of solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger the surface area for a given mass of particles. Examples of heterogeneous catalysis
Habers Process

Preparation of sulphuric acid by contact process

Manufacture of methyl alcohol from CO and H2 using (ZnO+Cr2O3) as catalyst

Homogeneous Catalysts
Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles invoked in heterogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a solvent with the substrates. One example of homogeneous catalysis involves the influence of H+ on the esterification of esters. H2SO4

CH3COOH + C2H5OH

CH3COOC2H5 + H2O

Biocatalysts - Enzymes
All of the reactions that take place within living bodies occur naturally, whether or not a catalyst is present. But they take place so slowly on their own that they are of no value to the survival of an organism. For example, if a sugar cube is placed in a glass of water, it eventually breaks down into simpler molecules with the release of energy. But that process might take years. A person who ate a sugar cube and had to wait that long for the energy to be released in the body would die. Fortunately, our bodies contain enzymes that speed up such reactions. They make it possible for the energy stored in sugar molecules to be released in a matter of minutes.

Properties of Catalysts
Properties can be classified as
Physical : Include surface area, pore structure, density etc .

Chemical : Include chemical state of the active catalyst phase, acidity and surface composition and structure.

Dynamic : Focus on catalyst behavior during reaction. These include activity and selectivity.

Characteristics of Catalysts
High activity per unit of volume in the eventual reactor. High selectivity towards the desired product at the conversion levels used in the eventual reactor, and the lowest possible selectivity to byproducts that generate waste problems. Sufficiently long life time with respect to deactivation. Possibility to regenerate, particularly if deactivation is fast. Sufficient thermal stability against sintering, structural change or volatilization inside the reaction environment. High mechanical strength with respect to crushing (e.g. under the weight of the catalyst bed or during the shaping process). High attrition resistance.

Catalyst Materials
These include Active Phase : The site where the reaction takes place. Support/Carrier : The catalyst is dispersed on a second material that enhances the effectiveness of the catalyst. This is called a carrier. Sometimes the carrier is merely a surface upon which the catalyst is spread to increase the surface area. More often, the support and the catalyst interact, affecting the catalytic reaction. Promoter : Chemical promoters may be added to the catalyst to optimize its activity and/or selectivity, and structural promoters may be incorporated to improve the mechanical properties and stabilize the particles against sintering.

Catalyst Characterization Techniques

Characterization is an important field in catalysis. In a proper catalytic study, as much as possible should be learned about the physical properties of the catalyst employed. Using appropriately prepared samples, TEM (traveling electron microscope) in its various modes (SEM, HREM) can routinely resolve metal crystallites and clusters down to sizes at the atomic level below 5 A (0.5 nm); consequently, a full particle size distribution can be obtained.

Provided a material is sufficiently crystalline to diffract X rays and is present in an amount greater than 1%, X-Ray Diffraction can be used for qualitative and quantitative analysis. The angles of diffraction differ for the various planes within the crystal. Thus, every compound or element has its own somewhat unique diffraction pattern. Also ,the larger the crystals of a given component, the sharper the peaks on the XRD pattern for each crystal plane.
The most sensitive techniques to count metal surface atoms are those involving selective chemisorption methods because all surface atoms, independent of crystallite size, are probed at the molecular level.

Catalyst Synthesis Techniques

Precipitation Sol gel Method Combustion synthesis Adsorption Ion exchange Wet Impregnation Reactive grinding

Use of Citric acid

Precipitation & Co-Precipitation

The objective of this method is to precipitate the catalyst precursor in the form of a hydroxide or carbonate in the pores and on the surface of the carrier by adjusting the pH of the metal salt solution-support slurry through addition of a base such as NaOH, NH4OH etc. Alternatively, support and catalyst precursor are co-precipitated together, such as coprecipitation of Ni hydroxide on silica by pouring together aqueous solutions of sodium silicate and nickel nitrate. Base and metal salt are carefully chosen to avoid the presence of species in the final catalyst that might later act as poison, such as Na+. Precipitation of dissolved nickel or iron in the presence of ammonium hydroxide and alumina, for example, results in formation of metal hydroxides in the alumina pores, as well as nickel or iron aluminates on the surface of the support.

Generally, support in the form of pellets or powder is added to the salt solution, after which the alkali solution is usually added drop wise, accompanied by rapid stirring of the slurry. Upon addition of sufficient alkali solution, catalyst precursor sols precipitate in the pores and/or catalyst precursors are formed by reaction on the interior surfaces of the support.

It is highly desirable to obtain uniform, finely divided deposits, since this will ultimately translate to a highly dispersed, high surface area catalyst of high activity. Control of the precipitation rate inside the catalyst is a key to obtaining uniform, well-dispersed precipitate. This control is greatly facilitated by using urea. Urea, which is water soluble, hydrolyzes slowly at 90 C to form highly uniform concentrations of hydroxide at the support surface. As the hydrolysis is slow but precipitation is rapid, hydroxyl groups are used as rapidly as they form, and the pH of the solution remains constant. After precipitation, the precursor-support is generally washed to remove undesirable soluble ions, dried, and finally calcined to decompose the catalyst precursor. The temperature required for calcination may vary considerably with different catalyst precursor support combinations. Catalyst preparation by precipitation is the preferred route to achieve moderately high to high loadings at reasonably high dispersions. When properly conducted, it favours uniform distribution of the active precursor on the support in a well-dispersed phase. A possible disadvantage is that some base metal catalyst precursor species formed during precipitation, such as Ni silicate or Ni aluminate, are oxidized or reduced to the desired active phase only under severe conditions.

References
Fundamentals of Industrial Catalytic Processes, Second edition, C. H. Bartholomew and R. J. Farrauto Pages 12-15,52-54,61-68,78-90,90-106 Concepts of Modern Catalysis and Kinetics, Wiley Publication I. Chorkendorff, J.W. Niemantsverdriet Page 181 Kinetics of Catalytic Reactions M. Albert Vannice Pages 14-31 Methods for preparation of catalytic materials James A. Schwarz, Cristian Contescu and Adriana Contescu Pages 479-490

References
www.files.chem.vt.edu/RVGS/ACT/notes/catalysts.html

www.tutorvista.com/search/properties-of-catalysts

www.britannica.com/EBchecked/topic/99128/catalyst

en.wikipedia.org/wiki/Catalyst

www.scienceclarified.com/Ca-Ch/Catalyst-and-Catalysis.html

Definitions
Activity : The increase in the rate of a specified chemical reaction caused by an enzyme or other catalyst. Selectivity : The relative activity of a catalyst in reference to a particular compound in a mixture. Sintering : Sintering is the bonding together of compacted powder particles at temperatures below the melting point. Precursor : a compound that participates in the chemical reaction that produces another compound.