‘‘catalysis by nano sulfated titania modified by transition metals"

in the present study, we have prepared and evaluated the physical and chemical properties and catalytic activities of transition metal loaded sulfated titania via the sol-gel route. Sol-gel method is widely used for preparing porous materials having controlled properties and leads to the formation of oxide particles in nano range, which are spherical or interconnected to each other. Characterization using various physico-chemical techniques and a detailed study of acidic properties are also carried out. Some reactions of industrial importance such as Friedel-Crafts reaction, fen-butylation of phenol,Beckmann rearrangement of cyclohexanone oxime, nitration of phenol and photochemical degradation of methylene blue have been selected for catalytic activity study in the present venture. The work is organized into eight chapters

Alkylation of Benzene with I-Octene over Titania Pillared Monmorillonite

Linear alkylbenzene sulfonic acid, the largest-volume synthetic surfactant, in addition to its excellent performance , is important due to its biodegradable environmental friendliness, as it has a straight chain and is prepared by the sulphonation of linear alkylbenzenes (LAB). To ensure environmental protection, the commercial benzene alkylation catalysts HF or AICI3 are replaced and we have developed a clean LAB production process using a pillared clay catalyst capable of not only replacing the conventional homogeneous catalyst, but also having high selectivity for the best biodegradable 2-phenyl LAB isomer .Pillared clay catalysts having high Bronsted acidity show efficient conversion in gas phase alkylation of benzene with 1-octene with a good 2-phenyl octane selectivity.

Alkylation of phenol with methanol over mixed oxides of tin with some rare earth elements

Alkylation of phenol with methanol has been carried out over Sn-La and Sn-Sm mixed oxides of varying compositions at 623 K in a vapour phase flow reactor. It is found that the product selectivity is greatly influenced by the acid-base properties of the catalysts. Ortho-cresol formation is favoured over catalysts with weak acid sites whereas formation of 2,6-xylenol occurs in the presence of stronger acid sites. The cyclohexanol decomposition reaction and titrimetric method using Hammett indicators have been employed to elucidate the acid-base properties of the catalysts.

Catalysis of C-alkylation of phenol using V2O5-La2O3 system

Vapour phase methylation of phenol is carried out over La2O3 supported vanadia systems of various composition. The structural features and physico chemical characterisation of the catalysts are investigated. Orthovanadates are formed in addition to surface vanadyl species on the metal oxide support. No V2O5 crystallites are detected. The acid base properties of the oxides are studied by Hammett indicator method and decomposition of cyclohexanol.The data are correlated with the catalytic activity and selectivity of the products. Ring alkylation is found to be predominant over these catalysts.

A comparative study on aniline alkylation activity using methanol and dimethyl carbonate as the alkylating agents over Zn–Co–Fe ternary spinel systems

The catalyst compositions of the Zn1−xCOxFe2O4 (x= 0, 0.2, 0.5, 0.8 and 1.0) spiel series possessing ‘x’ values, x less than or equal to 0.5, are unique for selective N-monomethylation of aniline using methanol as the alkylating agent. Since dimethyl carbonate (DMC) is another potential non-toxic alkylating agent, alkylation of aniline was investigated over various Zn–Co ferrites using DMC as the alkylating agent. The merits and demerits of the two alkylating agents are compared. Catalytic activity followed a similar trend with respect to the composition of the ferrospinel systems. DMC is active at comparatively low temperature, where methanol shows only mild activity. However, on the selectivity basis, DMC as an alkylating agent could not compete with methanol, since the former gave appreciable amounts of N,N-dimethylaniline (NNDMA) even at low temperature where methanol gave nearly 99% N-methylaniline (NMA) selectivity. As in the case of methanol, DMC also did not give any C-alkylated products.

Selective alkylation of aniline to N-methyl aniline using chromium manganese ferrospinels

Various compositions of chromium manganese ferrospinels were tested as catalysts for the vapour phase alkylation of aniline with methanol. The samples were prepared by room temperature co-precipitation technique and characterized by various physico-chemical methods. The acidity–basicity determination revealed that the samples possess greater amount of basic sites than acidic sites. All the ferrite samples proved to be selective and active for N-monoalkylation of aniline leading to N-methyl aniline; Cr0.6Mn0.4Fe2O4, Cr0.8Mn0.2Fe2O4 and CrFe2O4 exhibited cent percent selectivity for N-methyl aniline. Neither C-alkylated products nor any other side products were detected for all catalyst samples. The catalytic activity of the samples studied in this reaction is related to their acid–base properties and also on the cation distribution. Under the optimized reaction conditions all the systems showed constant activity for a long duration.

A comparative study of medium and large pore zeolites in alkylation reactions

In this thesis an attempt has been made to compare the catalytic activity of some medium and large pore zeolites in a few alkylation and acylation reactions. The work reported in the present study is basically centered around the following zeolites namely, ZSM-5, mordenite, zeolite Y and beta. The major reactions carried out were benzoylation of o-xylene, propionylation of toluene and anisole and benzylation of 0xylene.The programme involves the synthesis, modifications and characterization of the zeolite catalysts by various methods. The influence of various parameters such as non-framework cations, Si/AI ratio of zeolites, temperature of the reaction, catalyst concentration, molar ratio of the reactants and recycling of the catalysts were also examined upon the conversion of reactants and the formation of the desired products in the alkylation / acylation reactions.The general conclusions drawn by us from the results obtained are summarized in the last chapter of the thesis. Zeolite beta offers interesting opportunities as a potential catalyst in alkylation reactions and the area of catalysis by medium and large pore zeolites is very fascinating and there is plenty of scope for further research in this field. Moreover, zeolite based catalysts are effective in meeting current industrial processing and more stringent environment pollution limits.

Influence of residual cations (Na+, K+ and Mg2+) in the alkylation activity of benzene with 1-octene over rare earth metal ion exchanged FAU–Y zeolite

The effect of residual cations in rare earth metal modified faujasite–Y zeolite has been monitored using magic angle spinning NMR spectral analysis and catalytic activity studies. The second metal ions being used are Na+, K+ and Mg+. From a comparison of the spectra of different samples, it is concluded that potassium and magnesium exchange causes a greater downfield shift in the 29Si NMR peaks. Also, lanthanum exchanged samples show migration behavior from large cages to small cages, which causes the redistribution of second counter cations. It is also observed that Mg2+ causes the most effective migration of lanthanum ions due to its greater charge. The prepared systems were effectively employed for the alkylation of benzene with 1-octene in the vapor phase. From the deactivation studies it is observed that the as-exchanged zeolites possess better stability towards reaction condition over the pure HFAU zeolite.

Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds

Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involves catalysis.Solid acid catalysts are appealing since the nature of acid sites is known and their chemical behavior in acid catalyzed reactions can be rationalized by means of existing theories and models. Mixed oxides crystallizing in spinel structure are of special interest because the spinel lattice imparts extra stability to the catalyst under various reaction conditions so that theses systems have sustained activities for longer periods. The thesis entitled" Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds " presents the preparation ,characterization ,and activity studies of the prepared spinels were modified by incorporating other ions and by changing the stoichiometry.The prepared spinels exhibiting better catalytic activity towards the studied reactions with good product selectivity.Acid-base properties and cation distribution of the spinels were found to control the catalytic activity.

Studies on Polymer Bound Antioxidants

The primary aim of this work has been to prepare efficient and cost effective polymer bound antioxidants by direct’ attachment of conventional antioxidants to a modified polymer. Due to the importance and easy availability of natural rubber in Kerala, it is proposed to make use of low molecular weight natural rubber as the polymer substrate for binding the antioxidant in most cases. The molecular weight of such low molecular weight natural rubber can be easily manipulated by varying the time of mastication, UV—irradiation etc. Further, the bound antioxidant may also get vulcanized during the vulcanization of the elastomer to which it is added, making the antioxidant non—volatile and non extractable. Several methods are proposed to be investigated for attaching the antioxidant to the low molecular weight natural rubber such as modified Friedel-Craft's alkylation reaction, binding during UV—irradiation, binding during aggressive mastication etc. The efficiency of such rubber bound antioxidants is proposed to be compared with that of conventional antioxidants in terms of volatility, extractability in solvents, ageing resistance etc. Naturally occuring antioxidants such as cardanol, are also proposed to be modified by binding them to low molecular weight natural rubber. The study is undertaken with the intention of generating a class of bound antioxidants which can be used in elastomers for aggressive and long term application.

“A comparative study of medium and large pore zeolites in alkylation reactions”

Zeolites have established themselves as industrial catalysts for over two decades for a variety of hydrocarbon processing reactions where acidity and shape selectivity are important factors. As solid catalysts, zeolites may be advantageous and superior compared to their homogenous counterparts due to their characteristic properties. It is only in recent years that the utility of zeolites for organic synthesis is recognized for producing specific organic intermediates and fine chemicals in high selectivity. In this thesis an attempt has been made to compare the catalytic activity of some medium and large pore zeolites in a few alkylation and acylation reactions. The work reported in the present study is basically centered around the following zeolites namely, ZSM-5, mordenite, zeolite Y and beta. The major reactions carried out were benzoylation of o-xylene, propionylation of toluene and anisole and benzylation of oxylene. . The programme involves the synthesis, modifications and characterization of the zeolite catalysts by various methods. The influence of various parameters such as non-framework cations, Si/Al ratio of zeolites, temperature of the reaction, catalyst concentration, molar ratio of the reactants and recycling of the catalysts were also examined upon the conversion of reactants and the formation of the desired products in the alkylation/ acylation reactions. The general conclusions drawn by us from the results obtained are summarized in the last chapter of the thesis. Zeolite beta ofi'ers interesting opportunities as a potential catalyst in alkylation reactions and the area of catalysis by medium and large pore zeolites is very fascinating and there is plenty of scope for further research in this field. Moreover, zeolite based catalysts are effective in meeting current industrial processing and more stringent environment pollution limits.

Short Isora Fibre Reinforced Natural Rubber Composites

The present study deals with the short isora fibre reinforced natural rubber composites. In recent years there has been a tremendous advancement in the field of science and technology of short fibre reinforced polymer composites. The low density, high strength, high stiffness to weight ratio, excellent durability and design flexibility are the primary reasons for their use in many diversified fields such as air crafts, automobiles, marine industry etc. Compared to the various natural and synthetic fibres used as reinforcement for elastomer composites isora fibre is superior in many aspects. `Isora' is a natural lignocellulosic fibre which is easily available in South India especially in Kerala. The fibre is separated from the bark of the Helicteres isora plant by retting process. This fibre has excellent mechanical properties and is easily amenable to physical and chemical modifications. The study shows that composites with poor interfacial bonding tend to dissipate more energy than that with to interfacial bonding. The mechanical loss also can be related to interfacial bonding. The effect of chemical treatment of isora fibre on damping was also studied. Both in the low and high temperature region which indicates that this composite posseses low damping and hence good interfacial bonding characteristics. Hence these composites are better candidates for high damping applications. Composites with longitudinally oriented fibres showed high storage modulus than transversely oriented ones due to the effective stress transfer between fibre and matrix.

Acidity and catalytic activity of rare earth modified Al/Zr pillared clays

The pillared montmorillonite has been prepared by exchanging Na+ in the interlayer of montmorillonite with Al hydroxy cation followed by calcination. Pillared clays are also prepared after exchanging Na' ions with Ce, La, Sm-ions and then pillarcd with aluminium oxides, The surface characterisation of the prepared catalysts has been done using XRD and surface area measurements. To probe the acidic property of the system, temperature programmed desorption (TPD) of NH, has been done. Toluene alkylation by benzyl chloride has been carried out for the evaluation of catalytic activity. The most active system is found to be mixed Al/Zr pillarcd montrnorillonite.

A comparative study on the anisole methylation activity of lanthanum-promoted Sn02 catalyst and its sulfate-doped analogue

A comparative study on the anisole methylation with methanol over lanthanum-promoted Sn02 catalyst and its sulfate-doped analogue is presented. A maximum 2.6-xylenol selectivity of 82% was achieved at 400 degreeC under optimized conditions at an anisole conversion of 65% over lanthanum-promoted Sn02 catalyst. The sulfate modification resulted in the dealkylation of anisole to phenol followed by several unselective side reactions due to the creation of strong acid sites. The activity of lanthanum-modified tin oxide catalysts in the selective formation of 2.6-xylenol is ascribed to the presence of weak Lewis acid sites and comparatively stronger basic sites.