Zeolite Encapsulated Complexes Of Fe,Co,Ni,Cu And Pd:Synthesis , Characterization And Catalysis-2003

This thesis deals with the synthesis, characterization and catalysis activity studies of some zeolite encapsulated complexes. Encapsulation inside the zeolite cages makes the catalysts more stable. Further, the framework prevents the complexes from dimerising. Catalysis by metal complexes encapsulated in the cavities of zeolites and other molecular sieves has many features of homogeneous, heterogenous and enzymatic catalysis. Serious attempts has been made to gain product selectivity in catalysis .The catalytic activity shown by the encapsulated complexes can be correlated to the structure of the active site inside the zeolite pore. It deals with the studies on the partial oxidation of benzyl alcohol to benzaldehyde. The oxidatio was carried out using hydrogen peroxide as oxidant in presence of PdYDMG and CuYSPP as catalysts. The product (benzaldehyde) was detected using TLC and confirmed using GC.The catalytic activity of the complexes was tested for oxidation under various conditions. The operating conditions like the amount of the catalyst, reaction time, oxidant to substrate ratio, reaction temprature, and solvents have been optimized. No further oxidation products were obtained on continuing the reaction for four hours beyond the optimum time. Maximum conversion was obtained at room temperature and the percentage conversion decreased with increase in temperature. Activity was found to be dependent on the solvent used. With increasing awareness about the dangers of environmental degradation, research in chemistry is getting increasing geared to the development of “green chemistry,” by designing environmentally friendly products and processes that bring down the generation and use of hazardous substances.

Investigation of Offences against National Security

The study is a close scrutiny of the process of investigation of offences in India along with an analysis of powers and functions of the investigating agency. The offences, which are prejudicial to sovereignty, integrity and security of the nation or to its friendly relations with foreign states, are generally called the offences against national security. Offences against national security being prejudicial to the very existence of the nation and its legal system, is a heinous and terrible one. As early as 1971 the Law Commission of India had pointed out the need of treating the offences relating to national security and their perpetrators on a totally different procedural footing. The recommendation that, all the offences coming under the said category ought to be brought under the purview of a single enactment so as to confront such offences effectively. The discrepancies in and inadequacies of the criminal justice system in India as much as they are related to the investigations of the offences against national security are examined and the reforms are also suggested. The quality of criminal justice is closely linked with the caliber of the prosecution system and many of the acquittals in courts can be ascribed not only to poor investigations but also to poor quality of prosecution.

Production and Characterization of Endocylanase from Bacillus Pumilus Using Solidstate Fermentation and its Application in 'Paper Pulp Processing

In the present studies it is clear that Bacillus pumilus xylanase is having the characteristic suited for an industrial enzyme (xylanases that are active and stable at elevated temperatures and alkaline pH are needed). SSF production of xylanases and its application appears to be an innovative technology where the fermented substrate is the enzyme source that is used directly in the bleaching process without a prior downstream processing. The direct use of SSF enzymes in bleaching is a relatively new biobleaching approach. This can certainly benefit the bleaching process to lower the xylanase production costs and improve the economics and viability of the biobleaching technology. The application of enzymes to the bleaching process has been considered as an environmentally friendly approach that can reduce the negative impact on the environment exerted by the use of chlorine-based bleaching agents. It has been demonstrated that pretreatment of kraft pulp with xylanase prior to bleaching (biobleaching) can facilitate subsequent removal of lignin by bleaching chemicals, thereby, reducing the demand for elemental chlorine or improving final paper brightness. Using this xylanase pre-treatment, has resulted in an increased of brightness (8.5 Unit) when compared to non-enzymatic treated bleached pulp prepared using identical conditions. Reduction of the consumption of active chlorine can be achieved which results in a decrease in the toxicity, colour, chloride and absorbable organic halogen (AOX) levels of bleaching effluents. The xylanase treatment improves drainage, strength properties and the fragility of pulps, and also increases the brightness of pulps. This positive result shows that enzyme pre-treatment facilitates the removal of chromophore fragments of pulp there by making the process more environment friendly

Development of Bioreactors for Nitrifying Water In Closed System Hatcheries Of Penaeid And Non-Penaeid Prawns

In the present study the development of bioreactors for nitrifying water in closed system hatcheries of penaeid and non-penaeid prawns. This work is an attempt in this direction to cater to the needs of aquaculture industry for treatment and remediation of ammonia and nitrate in penaeid and non-penaeid hatcheries, by developing nitrifying bacteria allochthonous to the particular environment under consideration, and immobilizing them on an appropriately designed support materials configured as reactors. Ammonia toxicity is the major limiting factors in penaeid and non-penaeid hatchery systems causing lethal and sublethal effects on larvae depending on the pH values. Pressing need of the aquaculture industry to have a user friendly and economically viable technology for the removal of ammonia, which can be easily integrated to the existing hatchery designs without any major changes or modifications. Only option available now is to have biological filters through which water can be circulated for the oxidation of ammonia to nitrate through nitrite by a group of chemolithotrophs known as nitrifying bacteria. Two types of bioreactors have been designed and developed. The first category named as in situ stringed bed suspended bioreactor(SBSBR) was designed for use in the larval rearing tanks to remove ammonia and nitrite during larval rearing on a continuous basis, and the other to be used for nitrifying freshly collected seawater and spent water named as ex situ packed bed bioreactior(PBBR). On employing the two reactors together , both penaeid and non-penaeid larval rearing systems can be made a closed recirculating system at least for a season. A survey of literature revealed that the in situ stringed bed suspended reactor developed here is unique in its design, fabrication and mode of application.

Acetalization of ketones on K-10 clay and rare earth exchanged HFAU-Y zeolites: A mild and facile procedure for the synthesis of dimethylacetals

Dimethylacetals of ketones; cyclohexanone, acetophenone, and benzophenone have been prepared by reacting ketones with methanol under mild reaction conditions. Large pore zeolites (H-Y and its rare earth metal, Ce3+, La3+, and RE3+ modified forms), and mesoporous clay (K-10 montmorillonite and its cerium exchanged counterpart) with regular pore structure, silica and silica-alumina have been used as catalysts. Clay catalysts are found to be much more active than zeolites, thanks to slightly bigger pore size. The nature of the pores of the solid acid catalysts determine acetalization efficiency of a particular catalyst. As evidenced by the reaction time studies, the catalyst decay is greater over the zeolites than over the clays. Carrying out the reaction with ketones of different molecular sizes it is shown that K-10 clays and rare earth exchanged H-Y zeolites are promising environmentally friendly catalysts for their use in the production fine chemicals.

Studies on adhesives for bonding rubber to rubber and rubber to textiles

The primary objective of this investigation has been to develop more efficient and low cost adhesives for bonding various elastomer combinations particularly NR to NR, NR/PB to NR/PB, CR to CR,NR to CR and NR to NBR.A significant achievement of the investigation was the development of solventless and environment friendly solid adhesives for NR to NR and NR/PB to NR/PB particularly for precured retreading. Conventionally used adhesives in this area are mostly NR based adhesive strips in the presence of a dough. The study has shown that an ultra accelerator could be added to the dough just before applying it on the tire which can significantly bring down the retreading time resulting in prolonged tire service and lower energy consumption. Further latex reclaim has been used for the preparation of the solid strip which can reduce the cost considerably.Another significant finding was that by making proper selection of the RF resin, the efficiency and shelflife of the RFL adhesive used for nylon and rayon tire cord dipping can be improved. In the conventionally used RFL adhesive, the resin once prepared has to be added to the latex within 30 minutes and the RFL has to be used after 4 hours maturation time maximum shelf life of the RFL dip solution being 72 hours. In this study a formaldehyde deficient resin was used and hence more flexibility was available for mixing with latex and maturing. It also has a much longer shelf life. In the method suggested in this study, formaldehyde donors were added only in the rubber compound to make up the formaldehyde deficiency in the RFL. The results of this investigation show that the pull through load by employing this method and the conventional method are comparable. This study has also shown that the amount of RF resin with RFL adhesive can be partially replaced by other modifying agents for cost reduction.Cashew nut shell liquid (CNSL) resin can be employed for improving the bonding of dipped nylon and rayon cord with NR.Since CNSL resin cannot be added in the dip solution since it is not soluble in water, it was added in the rubber compound. The amount of wood rosin in the rubber compound can be reduced by using CNSL resin.Another interesting result of the investigation was the use of CR based adhesive modified with chlorinated natural rubber for CR to CR bonding. Addition of chlorinated natural rubber was found to improve sea water resistance of CR based adhesive. In the bonding of a polar rubber like nitrile rubber or polychloroprene rubber to a non polar rubber like natural rubber, an adhesive based on polychloroprene rubber was found to be effective.

Sulfated titania mediated regioselective nitration of phenol in solid state

Titania, sulfated titania and chromium loaded sulfated titania were prepared by sol–gel method and characterized using different technique. Phenol is nitrated regioselectively by nitric acid using chromium loaded sulfated titania catalysts. A remarkable ortho selectivity is observed in solid state nitration to yield exclusively ortho-nitrophenol. Compared to the conventional process, phenol nitration over solid acid catalyst is a clean and environment friendly process. Catalytic activity well correlates with the Brönsted acid sites of these catalysts.

Development of Best Practices for Ship Recycling Processes

Ship recycling has been considered as the best means to dispose off an obsolete ship. The current state of art of technology combined with the demands of sustainable developments from the global maritime industrial sector has modified the status of erstwhile ‘ship breaking’ involving ship scrap business to a modern industry undertaking dismantling of ships and recycling/reusing the dismantled products in a supply chain of pre owned product market by following the principles of recycling. Industries will have to formulate a set of best practices and blend them with the engineering activities for producing better quality products, improving the productivity and for achieving improved performances related to sustainable development. Improved performance by industries in a sustainable development perspective is accomplished only by implementing the 4E principles, ie.,. ecofriendliness, engineering efficiency, energy conservation and ergonomics in their core operations. The present study has done a comprehensive investigation into various ship recycling operations for formulating a set of best practices.Being the ultimate life cycle stage of a ship, ship recycling activities incorporate certain commercial procedures well in advance to facilitate the objectives of dismantling and recycling/reusing of various parts of the vessel. Thorough knowledge regarding these background procedures in ship recycling is essential for examining and understanding the industrial business operations associated with it. As a first step, the practices followed in merchant shipping operations regarding the decision on decommissioning have been and made available in the thesis. Brief description about the positioning methods and important preparations for the most feasible ship recycling method ie.,. beach method have been provided as a part of the outline of the background information. Available sources of guidelines, codes and rules & regulations for ship recycling have been compiled and included in the discussion.Very brief summary of practices in major ship recycling destinations has been prepared and listed for providing an overview of the global ship recycling activities. The present status of ship recycling by treating it as a full fledged engineering industry has been brought out to establish the need for looking into the development of the best practices. Major engineering attributes of ship as a unique engineering product and the significant influencing factors on her life cycle stage operations have been studied and added to the information base on ship recycling. Role of ship recycling industry as an important player in global sustainable development efforts has been reviewed by analysing the benefits of ship recycling. A brief synopsis on the state of art of ship recycling in major international ship recycling centres has also been incorporated in the backdrop knowledgebase generation on ship recycling processes.Publications available in this field have been reviewed and classified into five subject categories viz., Infrastructure for recycling yards and methods of dismantling, Rules regarding ship recycling activities, Environmental and safety aspects of ship recycling, Role of naval architects and ship classification societies, Application of information technology and Demand forecasting. The inference from the literature survey have been summarised and recorded. Noticeable observations in the inference include need of creation of a comprehensive knowledgebase on ship recycling and its effective implementation in the industry and the insignificant involvement of naval architects and shipbuilding engineers in ship recycling industry. These two important inferences and the message conveyed by them have been addressed with due importance in the subsequent part of the present study.As a part of the study the importance of demand forecasting in ship recycling has been introduced and presented. A sample input for ship recycling data for implementation of computer based methods of demand forecasting has been presented in this section of the thesis.The interdisciplinary nature of engineering processes involved in ship recycling has been identified as one of the important features of this industry. The present study has identified more than a dozen major stake holders in ship recycling having their own interests and roles. It has also been observed that most of the ship recycling activities is carried out in South East Asian countries where the beach based ship recycling is done in yards without proper infrastructure support. A model of beach based ship recycling has been developed and the roles, responsibilities and the mutual interactions of the elements of the system have been documented as a part of the study Subsequently the need of a generation of a wide knowledgebase on ship recycling activities as pointed out by the literature survey has been addressed. The information base and source of expertise required to build a broad knowledgebase on ship recycling operations have been identified and tabulated. Eleven important ship recycling processes have been identified and a brief sketch of steps involved in these processes have been examined and addressed in detail. Based on these findings, a detailed sequential disassembly process plan of ship recycling has been prepared and charted. After having established the need of best practices in ship recycling initially, the present study here identifies development of a user friendly expert system for ship recycling process as one of the constituents of the proposed best practises. A user friendly expert system has been developed for beach based ship recycling processes and is named as Ship Recycling Recommender (SRR). Two important functions of SRR, first one for the ‘Administrators’, the stake holders at the helm of the ship recycling affairs and second one for the ‘Users’, the stake holders who execute the actual dismantling have been presented by highlighting the steps involved in the execution of the software. The important output generated, ie.,. recommended practices for ship dismantling processes and safe handling information on materials present onboard have been presented with the help of ship recycling reports generated by the expert system. A brief account of necessity of having a ship recycling work content estimation as part of the best practices has been presented in the study. This is supported by a detailed work estimation schedule for the same as one of the appendices.As mentioned earlier, a definite lack of involvement of naval architect has been observed in development of methodologies for improving the status of ship recycling industry. Present study has put forward a holistic approach to review the status of ship recycling not simply as end of life activity of all ‘time expired’ vessels, but as a focal point of integrating all life cycle activities. A new engineering design philosophy targeting sustainable development of marine industrial domain, named design for ship recycling has been identified, formulated and presented. A new model of ship life cycle has been proposed by adding few stages to the traditional life cycle after analysing their critical role in accomplishing clean and safe end of life and partial dismantling of ships. Two applications of design for ship recycling viz, recyclability of ships and her products and allotment of Green Safety Index for ships have been presented as a part of implementation of the philosophy in actual practice.

Design and Development of Instrumentation Systems to determine the Dry Rubber Content in Natural Rubber Latex

Hevea latex is a natural biological liquid of very complex composition .Besides rubber hydrocarbons,it contains many proteinous and resinous substances,carbohydrates,inorganic matter,water,and others.The Dry Rubber Content (DRC) of latex varies according to season, tapping system,weather,soil conditions ,clone,age of the tree etc. The true DRC of the latex must be determined to ensure fair prices for the latex during commercial exchange.The DRC of Hevea latex is a very familiar term to all in the rubber industry.It has been the basis for incentive payments to tappers who bring in more than the daily agreed poundage of latex.It is an important parameter for rubber and latex processing industries for automation and verious decesion making processes.This thesis embodies the efforts made by me to determine the DRC of rubber latex following different analytical tools such as MIR absorption,thermal analysis.dielectric spectroscopy and NIR reflectance.The rubber industry is still Looking for a compact instrument that is accurate economical,easy to use and environment friendly.I hope the results presented in this thesis will help to realise this goal in the near future.

Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

Structural tuning of Montmorillonite clays by pillaring: Designing of shape selective solid acid catalysts and PANI - Montmorillonite nanocomposites

Green chemistry boots eco-friendly,natural clays as catalysts in the chemical as well as in the pharmaceutical industry.Industry demands thermal stability,mechanical strength etc for the catalyst and there the modification methods becomes important.Pillaring tunes clays as efficient catalytic templates for shape selective organic synthesis.Here pillared clays are used as promising alternatives for the environmentally hazardous homogeneous catalysts in some industrially important Friedel-Crafts alkylation reactions of arenes with lower alchohols and higher olefins.The layer structure is enhanced upon pillaring and allows the nanocomposite formation with polyaniline to develop today’s nanoscale diameter devices.Present work gives an entry of pillared clays to the world of conducting composite nanofibers.

Catalysis by Polymer Supported Dendrimers, their Metal Complexes and Nanoparticle Conjugates

The present thesis has described the development of some heterogeneous catalysts based on polymer supported dendrimers. Attachment of dendrimers to crosslinked polymer produced new catalysts with combined benefits of both dendrimers and heterogeneous catalysts. These were used as heterogeneous catalysts in selected reactions. All possible attempts were taken to avoid halogenated and aromatic solvents and toxic reagents. In short the present work has dealt with development of environmental friendly catalysts based on dendrimers.

Amorphous Selenium films using CBD: A Novel Selenisation technique for preparing lndium Selenide and Copper lndium Selenide Thin Films

In the present work, we describe our efforts to develop device quality CuInSe2, films through low cost, simple and eco-friendly hybrid techniques. The most important point to be highlighted here is that the method fully avoids the use of poisonous gases such as H2Se/Se vapour. Instead, selenisation is achieved through solid state reaction between amorphous selenium and polycrystalline metal layers resulting in both binary and ternary selenides. Thin films of amorphous selenium (a-Se) used for this is deposited using Chemical Bath Deposition (CBD). CulnSe2 films are prepared through the selenisation process. Another PV material, indium selenide (In2Se3) thin films are also prepared using this process.

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Study on Solid Waste Management : An Economic Analysis with Respect to Ernakulam District

This thesis analyzed waste generation and waster disposal problems in municipalities and Cochin Corporation in Ernakulam district.Then the potential of resource recovery and recycling from biodegradable and non bio-degradable waste is established.The study further focused on the need for segregation of waste at the source as biodegradable and non biodegradable solid waste.The potential of resource recovery is explained in detail through the case study.The thesis also highlights the economically viable and environmental friendly methods o f treatment of waste.But the problem is that concerted and earnest attempts are lacking in making use of such methods.In spite of the health problems faced,people living near the dump sites are forced to stay there either because of their weak economic background or family ties.The study did not calculate the economic cost of health problems arising out of unscientific and irresponsible methods of waste disposal.