Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

Novel cationic polymers for use at biological interfaces

One of the main problems with the use of synthetic polymers as biomaterials is the invasion of micro-organisms causing infection. A study of the properties of polymeric antibacterial agents, in particular polyhexamethylene biguanide, has revealed that the essential components for the design of a novel polymeric antibacterial are a balance between hydrophilicity and hydrophobicity coupled with sites of cationicity. The effect of cation incorporation on the physical properties of hydrogels has been investigated. Hydrogel systems copolymerised with either N-vinyl imidazole or dimethylaminoethyl methacrylate have been characterised in terms of their water binding, mechanical and surface properties. It has been concluded that the incorporation of these monomers does not adversely affect the properties of such hydrogels and that these materials are potential candidates for further development for use in biomedical applications. It has been reported that hydro gels with ionic character may increase the deposition of biological material onto the hydrogel surface when it is in contact with body fluids. An investigation into the deposition characteristics of hydrogels containing the potentially cationic monomers has been carried out, using specific protein adsorption and in vitro spoilation techniques. The results suggest that at low levels of cationicity, the deposition of positively charged proteins is reduced without adversely affecting the uptake of the other proteins. The gross deposition characteristics were found to be comparable to some commercially available contact lens materials. A preliminary investigation into the development of novel antibacterial polymers has been completed and some novel methods of bacterial inhibition discussed. These methods include development of an hydrogel whose potential application is as a catheter coating.

Hydrogels for dermal applications

This thesis is concerned with the development of hydrogels that adhere to skin and can be used for topical or trans dermal release of active compounds for therapeutic or cosmetic use. The suitability of a range of monomers and initiator systems for the production of skin adhesive hydro gels by photopolymerisation was explored and an approximate order of monomer reactivity in aqueous solution was determined. Most notably, the increased reactivity of N-vinyl pyrrolidone within an aqueous system, as compared to its low rate of polymerisation in organic solvents, was observed. The efficacy of a series of photoinitiator systems for the preparation of sheet hydrogels was investigated. Supplementary redox and thermal initiators were also examined. The most successful initiator system was found to be Irgacure 184, which is commonly used in commercial moving web production systems that employ photopolymerisation. The influence of ionic and non-ionic monomers, crosslinking systems, water and glycerol on the adhesive and dynamic mechanical behaviour of partially hydrated hydrogel systems was examined. The aim was to manipulate hydrogel behaviour to modify topical and transdermal delivery capability and investigated the possibility of using monomer combinations that would influence the release characteristics of gels by modifying their hydrophobic and ionic nature. The copolymerisation of neutral monomers (N-vinyl pyrrolidone, N,N-dimethyl acrylamide and N-acryloyl morpholine) with ionic monomers (2-acrylamido-2-methylpropane sulphonic acid; sodium salt, and the potassium salt of 3-sulphopropyl acrylate) formed the basis of the study. Release from fully and partially hydrated hydrogels was studied, using model compounds and a non-steroidal anti-inflammatory drug, Ibuprofen. Release followed a common 3-stage kinetic profile that includes an initial burst phase, a secondary phase of approximate first order release and a final stage of infinitesimally slow release such that the compound is effectively retained within the hydrogel. Use of partition coefficients, the pKa of the active and a knowledge of charge-based and polar interactions of polymer and drug were complementary in interpreting experimental results. In summary, drug ionisation, hydrogel composition and external release medium characteristics interact to influence release behaviour. The information generated provides the basis for the optimal design of hydrogels for specific dermal release applications and some understanding of the limitations of these systems for controlled release applications.

Synthesis of novel cylic monomers for hydrogel polymers

The aim of the project was to synthesise hydrophilic derivatives of 1,2-dihydroxy-3,5-cyclohexadiene (DHCD) and to copolymerise these derivatives with 2-hydroxyethyl methacrylate (HEMA), to give a completely new range of hydrogel materials. It was thought that hydro gels incorporating hydrophilic derivatives of DHCD could have good mechanical properties and good water binding ability. A model compound for cis-DHCD was sought, as cis-DHCD was expensive and stable under only a narrow range of conditions. Catechol was found to be an excellent model for cis-DHCD, as 1H NMR spectroscopy indicated that both compounds contained eclipsed hydroxy groups and flat rings. A number of catechol derivatives were prepared in good yield, under non-acidic conditions at room temperature. The limited availabilty of cis-DHCD led to an investigation into synthesising hydrophilic derivatives of both cis and trans-DHCD indirectly. Hydrophobic derivatives were easily prepared by indirect routes, but it was found that hydrophilic derivatives were considerably more difficult to synthesise. A number of novel routes to both cis and trans-DHCD were also explored. Copolymerisation of diacetate, dimethylcarbonate and dipivalate derivatives of cis-DHCD with HEMA, to form a hitherto unknown group of hydrogels, is reported. Hydrogels containing these monomers showed significant improvements in both tensile strength and Youngs modulus, at both equivalent composition and water content, over the corresponding HEMA / styrene and HEMA / methyl methacrylate analogues. It was observed that derivatives of trans-DHCD polymerise with difficulty. 1H NMR studies indicated that both faces of the ring were shielded by the pendant groups thereby preventing efficient polymerisation of the trans monomers.

Multi-function controllers for a hydraulic pump

This project has been undertaken for Hamworthy Hydraulics Limited. Its objective was to design and develop a controller package for a variable displacement, hydraulic pump for use mainly on mobile earth moving machinery. A survey was undertaken of control options used in practice and from this a design specification was formulated, the successful implementation of which would give Hamworthy an advantage over its competitors. Two different modes for the controller were envisaged. One consisted of using conventional hydro-mechanics and the other was based upon a microprocessor. To meet short term customer prototype requirements the first section of work was the realisation of the hydro-mechanical system. Mathematical models were made to evaluate controller stability and hence aid their design. The final package met the requirements of the specification and a single version could operate all sizes of variable displacement pumps in the Hamworthy range. The choice of controller options and combinations totalled twenty-four. The hydro-mechanical controller was complex and it was realised that a micro-processor system would allow all options to be implemented with just one design of hardware, thus greatly simplifying production. The final section of this project was to determine whether such a design was feasible. This entailed finding cheap, reliable transducers, using mathematical models to predict electro-hydraulic interface stability, testing such interfaces and finally incorporating a micro-processor in an interactive control loop. The study revealed that such a system was technically possible but it would cost 60% more than its hydro-mechanical counterpart. It was therefore concluded that, in the short term, for the markets considered, the hydro-mechanical design was the better solution. Regarding the micro-processor system the final conclusion was that, because the relative costs of the two systems are decreasing, the electro-hydraulic controller will gradually become more attractive and therefore Hamworthy should continue with its development.

Vertical and horizontal scope economies in the regulated US electricity power industry

This paper investigates vertical economies between generation and distribution of electric power, and horizontal economies between different types of power generation in the U.S. electric utility industry. Our quadratic cost function model includes three generation output measures (hydro, nuclear and fossil fuels), which allows us to analyze the effect that generation mix has on vertical economies. Our results provide (sample mean) estimates of vertical economies of 8.1% and horizontal economies of 5.4%. An extensive sensitivity analysis is used to show how the scope measures vary across alternative model specifications and firm types. © 2012 Blackwell Publishing Ltd and the Editorial Board of The Journal of Industrial Economics.

Measuring economies of horizontal and vertical integration in the US electric power industry:how costly is unbundling?

This research employs econometric analysis on a cross section of American electricity companies in order to study the cost implications associated with unbundling the operations of integrated companies into vertically and/or horizontally separated companies. Focusing on the representative sample average firm, we find that complete horizontal and vertical disintegration resulting in the creation of separate nuclear, conventional, and hydro electric generation companies as well as a separate firm distributing power to final consumers, results in a statistically significant 13.5 percent increase in costs. Maintaining a horizontally integrated generator producing nuclear, conventional, and hydro electric generation while imposing vertical separation by creating a stand alone distribution company, results in a lower but still substantial and statistically significant cost penalty amounting to an 8.1 % increase in costs relative to a fully integrated structure. As these results imply that a vertically separated but horizontally integrated generation firm would need to reduce the costs of generation by 11% just to recoup the cost increases associated with vertical separation, even the costs associated with just vertical unbundling are quite substantial. Our paper is also the first academic paper we are aware of that systematically considers the impact of generation mix on vertical, horizontal, and overall scope economies. As a result, we are able to demonstrate that the estimated cost of unbundling in the electricity sector is substantially influenced by generation mix. Thus, for example, we find evidence of strong vertical integration economies between nuclear and conventional generation, but little evidence for vertical integration benefits between hydro generation and the distribution of power. In contrast, we find strong evidence suggesting the presence of substantial horizontal integration economies associated with the joint production of hydro generation with nuclear and/or conventional fossil fuel generation. These results are significant because they indicate that the cost of unbundling the electricity sector will differ substantially in different systems, meaning that a blanket regulatory policy with regard to the appropriateness of vertical and horizontal unbundling is likely to be inappropriate.

A comparative molecular similarity indices (CoMSIA) study of peptide binding to the HLA-A3 superfamily

Epitope identification is the basis of modern vaccine design. The present paper studied the supermotif of the HLA-A3 superfamily, using comparative molecular similarity indices analysis (CoMSIA). Four alleles with high phenotype frequencies were used: A*1101, A*0301, A*3101 and A*6801. Five physicochemical properties—steric bulk, electrostatic potential, local hydro-phobicity, hydrogen-bond donor and acceptor abilities—were considered and ‘all fields’ models were produced for each of the alleles. The models have a moderate level of predictivity and there is a good correlation between the data. A revised HLA-A3 supermotif was defined based on the comparison of favoured and disfavoured properties for each position of the MHC bound peptide. The present study demonstrated that CoMSIA is an effective tool for studying peptide–MHC interactions.

Eco-efficiency considering the issue of heterogeneity among power plants

One of the main objectives in restructuring power industry is enhancing the efficiency of power facilities. However, power generation industry, which plays a key role in the power industry, has a noticeable share in emission amongst all other emission-generating sectors. In this study, we have developed some new Data Envelopment Analysis models to find efficient power plants based on less fuel consumption, combusting less polluting fuel types, and incorporating emission factors in order to measure the ecological efficiency trend. We then applied these models to measuring eco-efficiency during an eight-year period of power industry restructuring in Iran. Results reveal that there has been a significant improvement in eco-efficiency, cost efficiency and allocative efficiency of the power plants during the restructuring period. It is also shown that despite the hydro power plants look eco-efficient; the combined cycle ones have been more allocative efficient than the other power generation technologies used in Iran.