HETEROGENEOUS ACID CATALYSIS

Abstract- Acid catalysis has extreme importance in synthetic chemistry at laboratory and industrial level. But, use of conventional homogeneous acids generate significant amount of waste and affect the environment. So, people move toward solid acid catalysis and profitably replaced homogeneous catalysts with recyclable heterogeneous catalysts and made the processes eco-friendly. Silica supported acids provide one of the easiest way to prepare solid acid catalyst. Zeolites, hetero polyacids, ion exchange resins are also useful in heterogeneous catalysis. Sulphated transition metal oxide species like, sulphated zirconia, sulphated titania, sulphated tungstate found several application even in commercial level and has been receiving more attention from 2-3 decades because of their superior acid strength. This article mainly discus supported acid catalyst, Zeolites and sulphated zirconia.

Introduction
Acid catalyst has key role in most of industrial and laboratory processes; both, Bronsted and Lewis acid catalysts are important in synthetic chemistry. But, all these acid catalysts generate considerable amount of waste. Bronsted acids are used in many unit processes like sulphonation, nitration, diazotization etc. besides these several name reactions, protectiondeprotection reactions also uses bronsted acid. Lewis acids are usually electron deficient metal salts like aluminium chloride, ferric chloride, antimony fluoride, titanium chloride and tin chloride, which are capable to accept electrons from Lewis bases. The chemical industry uses them for a variety of electrophilic substitution reactions in aromatics. Homogeneous catalysts leads to several problems such as corrosion of equipment, hazards of handling the corrosive acids which are not reused, neutralization of the resulting reaction mass. If spent acids are allowed to discharge in environment, it affects the quality of soil for agricultural use, also affect plants and marine life. Even if the spent acid effluent is

chemically treated to restore its pH, it still results in the release of deleterious chemical wastes into the environment, as other chemicals would be present. Lewis acids need to be hydrolyzed
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during the work-up process after which the spent Lewis acids cannot be recovered. When discarded into the environment they release toxic cations. The biological oxygen demand (BOD), chemical oxygen demand (COD), and total dissolved solids (TDS) loads on effluent treatment plants become enormous. Since the prices of these fine chemicals are very high. Solid acid catalyst solved some of these problems. Heterogeneous catalyst has many advantages like ease in handling the reagent and storage, it can be recover and reuse so avoid problem of effluent disposal and thus reduce the operational cost. Provide ease in work-up the reaction, on completion of the reaction the solid catalyst is filtered for re-use and isolate the product from filtrate. In heterogeneous catalysis the reaction takes place at the interface between the catalysts and the less dense phase. In other words heterogeneous catalysis describes the enhancement in the rate of a chemical reaction brought about by the presence of an interface between two phases.

Supported Solid Acid Catalyst:

Adsorption of acidic reagent on to the suitable solid support is a simple method to prepare solid acid catalyst. Solid support should be insoluble in the solvent medium, and should have a large surface area in order to accommodate as many catalytic sites as possible. Clays were the first solid acid catalysts used in organic synthesis[3]. Some of the types of clays frequently used are Bentonite, Montmorillonite K10 and Montmorillonite-KSF. Silica and alumina constitute a group of polymeric oxides of silicon and aluminium respectively. They can also be obtained in mixed polymeric forms. There are several reactions reported with silica supported sulphuric acid. Some of them are listed below1) Three component Biginelli reaction in 1-butyl-3-methylimidazolium bromide

([bmim]Br) as ionic liquid (IL) in the presence of silica sulfuric acid (SSA) as solid acid catalyst at 100 C within less than 2 hours. [4] 2) Beckmann rearrangement of oximes in dried dioxane at room temperature by using silica supported sulphuric acid as a green catalyst. Excellent conversion and selectivity were acquired in the Beckmann rearrangement of cyclohexanone oxime. The catalyst system was recycled and reused.[5]
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3) A remarkable acceleration in the synthesis of substituted coumarins via Pechmann reaction catalyzed by silicagel supported sulfuric acid (H2SO4/silica gel) at 120 C in high yields under solvent-free reaction condition with short reaction times is described.
[6]

4) The Use of Silica Sulfuric Acid as an Efficient Catalyst for Deprotection of Trimethylsilyl Ethers to the Corresponding Alcohols under Mild and Heterogeneous Conditions. [7] 5) Silica Sulfuric Acid as an Efficient Catalyst for the Friedlnder Quinoline Synthesis from Simple Ketones and ortho-Aminoaryl Ketones Under Microwave Irradiation. [8] 6) Vapor-phase Nitration of Benzene to Nitrobenzene over Supported Sulfuric Acid Catalyst. [9] But, these supported acids have open or microporous structure. So, the total surface area available for catalysis is less and thus chemist move toward the mesoporous materials.

Zeolites
Zeolites are also known as molecular sieves. They are aluminosilicates with the general formula Nax[(AlO2)x(SiO2)y][H2O]y. They have a tetrahedral structure with each atom of silicon and aluminium surrounded by oxygen atoms. In natural samples, they have threedimensional crystalline microporous channels in which molecules of appropriate size can diffuse and react. The pore size in zeolites can be controlled using synthetic methods. In the zeolite structure four-bonded tetravalent silicon site is neutral whereas the four-bonded trivalent aluminium site is negative. This requires positively charged counter-ions such as Na+, as indicated in the general formula for zeolites. In order to make the zeolite acidic, sodium counterions are replaced with protons. This is done by first exchanging the sodium ions with ammonium ions and then heating the zeolite sample. On heating, NH3 is released and protons are left behind as the counter-ions, in place of sodium ions.

Zeolite with Na+ as a counter ion.

exchanging the sodium ions with ammonium ions

On heating, NH3 is released and protons are left behind as the counter-ions. As zeolite contain proton as a counter ion it act as a Bronsted acid. The ratio Si/Al determines the polarity, the acidity and the exchange capacity of the zeolites. These parameters also control the catalytic properties of zeolites. Such a zeolite network was first used by A. J. Houdry in the 1920s for isomerisation of straight-chain petroleum hydrocarbons to branched hydrocarbons.[3] This conversion process increased the octane number or the anti-knock property of gasoline. Table given below explain the effect of Si/Al ratio on surface area, micropore volume, Bronsted acid sites. (ref-23)
Sr No Sample Si/ Al ratio BET surface area 1 2 3 ZSM-5 Beta Y 39 27 2.6 370 490 810 Micro pore volume (m3/g) 0.13 0.18 0.32 Bronsted acid sites (mmol/g) 0.42 0.51 1.95

In zeolites, the active sites are protons and they are inside the pores (pore size < 8 ), and so the pore size places restriction on the shape and size of the molecule that can enter it. Bulky molecules cannot enter them. Therefore zeolites are useful in reactions involving either only small molecules or a mixture of different-sized molecules with the same functional group, where only the reaction of the smaller sized molecules is desired. Zeolites mordenite , ZSM-5, ZSM-11 , X , Y and beta have been studied and number of reactions are reported.[10, 11, 12, 13, 14]. Methods for characterizing Zeolites acidity were reviewed by W. E. Farneth and R. J. Gorte in Chem. Rev. 1995, 95, 615-635.

Sulphated ZirconiaIn last two- three decades much attention was paid on preparation and characterisation of zirconia based catalysts due to their superior catalytic activity for hydrocarbon conversions. [15] These catalysts are finding numerous applications in oil refinery and petrochemical industries. Among the promoted ZrO2 solid acid catalysts, the SO42/ ZrO2 become more popular due to its high activity for light alkane isomerizations even at low temperature.

a) Structure The composition and structure of the active component of sulfated zirconia remains as yet unclear even though a huge number of studies have dealt with the problem. [16-19] Although, much work has been done on lower alkanes isomerisation over sulfated zirconia catalyst, the effects of various chemical species such as hydrogen on the process efficiency are not properly understood [2]. It typically contains 56 wt % SO3 and consists of zirconia in a tetragonal nanocrystalline structure. Acidic character of sulphated zirconia is due to the sulphate species attached to zirconia surface.

b) Catalyst preparation Dissolve About 25 g of ZrOCl28H2O in doubly distilled water. To this clear solution, add dilute aqueous ammonia drop-wise from a burette with vigorous stirring until the pH of the solution reached 8. Wash the obtained precipited with distilled water until free from chloride ions and dry at 393K for 24 h. To prepare sulfated ZrO2 catalyst, grind a portion of the obtained
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hydrous zirconia sample to fine powder and immerse in 1M H2SO4 solution (30 ml) for 30 min. evaporate the excess water on a water-bath and dry the resulting sample in oven at 393K for 12 h and calcine at 923K for 4 h in air atmosphere and store in vacuum desiccator. For the purpose of comparison prepare an unpromoted ZrO2 by calcining the hydrous zirconia at 923K for 4 h in air atmosphere.[21]

c) Catalyst characterization In most of the reports surface and bulk properties of ZrO2 and SO42/ZrO2 catalysts were examined by various spectroscopic and nonspectroscopic techniques namely, X-ray powder diffraction, BET surface area, ammonia-TPD and Raman spectroscopy. [21] Thermogravimetric analysis (TGA) was carried to characterize sulfur content in the catalyst.[22]

The specific surface area of SO4 2/ZrO2 sample is higher than that of ZrO2. Ammonia-TPD results revealed two temperature maxima on both the samples indicating the presence of two different types of acids sites with different acid strength distribution [21]. The total amount of ammonia desorbed in the case of sulfated sample is much higher than that of pure ZrO2. It clearly indicates that impregnated sulfate ions show a strong influence on the acidic properties of the zirconia. The Raman spectrum of unprompted ZrO2 exhibited prominent bands due to a mixture of monoclinic (180, 188, 221, 331, 380, 476 and 637 cm1) and tetragonal (148, 290, 311, 454 and 647 cm1) phases and the bands due to tetragonal phase were less intense than the peaks due to monoclinic phase[21]. Whereas in the spectrum of sulfated zirconia catalyst bands representing the tetragonal phase were more intense.

The hydrous zirconia sample calcined at 923K is in poorly crystalline form with a mixture of monoclinic and tetragonal phases. On the other hand, the sulfated sample exhibits prominent lines due to tetragonal phase indicating that the adsorbed sulfate ions show a strong influence on the phase modification of zirconia from thermodynamically more stable monoclinic to the metastable tetragonal phase. [21, 23]

Ref-21

X-ray powder diffraction patterns of pure and sulfate promoted zirconia samples calcined at 923 K. ( ) Characteristic lines due to tetragonal zirconia; ( ) characteristic lines due to monoclinic zirconia. [21] d) Catalytic Activity: Sulphated zirconia act as efficient acid catalyst and many organic reactions for formation of pharmaceutically and biologically important molecules are reported with SZ. The significantly higher activity over that of the untreated metal oxides has been credited to the presence of sulfur (VI) species. Sulfur content of a sulfated zirconia catalyst strongly depend on its calcination temperature. Increase in calcination temperature usually results in the gradual removal of sulfur
from the catalyst surface. Main problem occur with this catalyst is the deactivation of sulphated

zirconia. Sulphur content of surface found to be decreases after each cycle with significant rate. Some reasons are given in literature for this deactivation of catalysta) Carbonaceous depositsDuring isomerisation of butane or pentane the alkene molecules are formed. These alkenes can then be dehydrogenated because of the strong acidity of the catalyst and form allylic species, oligomers, polymers and aromatics compounds. They are adsorbed on the catalyst surface and are blocking the active sites; resulting thus in the decrease of the catalytic activity.

b) WaterThe presence of excess amount of water act as poison for catalyst. the partial transformation of Lewis into Brnsted acidity in the presence of water is responsible for the deactivation of sulfated zirconia. But, this role of water is not firmly reported in literature.

c) Reduction of S(IV) to lower oxidation stateIsomerisation of lower alkanes proceeds through oxidative dehydrogenation results into formation of water and corresponding alkene. This ODH reduce sulfur to lower oxidation states. When transition metal is added to catalyst as a promoter, reduction of this metal suppose to be occur and avoid the deactivation of catalyst.

Phase changeOne more reason reported for deactivation of SZ is phase change. Zirconia is polymorphous material; monoclinic, tetragonal and cubic. The monoclinic phase is stable at room temperature. Sulphated zirconia mostly exist in tetragonal phase. Monoclinic sulphated zirconia has been reported to be 4-5 times less active than tetragonal sulphated zirconia. Li et al. claimed that the SZ deactivation is due to a surface phase change from tetragonal to monoclinic. They established a correlation between the deactivation of SZ catalysts after n-butane isomerization at 453 K with the zirconia phase change observed by recording UV Raman spectra. [25]

ConclusionDrawbacks involve in use of homogeneous catalyst leads to development of heterogeneous catalyst. This process begins with simple adsorption of acidic species on insoluble solid materials like clay, silica, alumina etc. But, comparatively lower acidic strength of heterogeneous catalysts force the chemist to study factors affecting acidic strengths and this leads to further improvement. For example, the co-relation between acidic strength and surface area of catalyst force the chemist to develop new catalyst with larger surface area. Increase in pore size of material results in to increase in surface area. A study deal with microporous, mesoporous and macro porous materials gives us new catalysts with enhanced acidic strength.

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