Biodiesel is rapidly growing as a fuel of interest due to the various advantages it has over conventional diesel fuel. While the pros – non-toxic, biodegradable, low green house gas emissions seem advantageous, the major issue that plagues the use of biodiesel is its cold weather operability. Biodiesel can present challenges in cold-weather operation, because certain of its constituent compounds can form precipitates in the fuel. These precipitates can cause undesired effects like plugging of fuel filters and deposits. This issue has been attributed to the presence of impurities (mostly saturated monoglycerides, di-glycerides, soap etc) in biodiesel and has been discussed in the literature. There is a move by users and standards associations to implement more stringent norms and quality control to avoid problems in the widespread use of biodiesel. This study involves ways to reduce MG’s in biodiesel by mitigating to a greater extent the possibility of side reactions (formation of soap). The effect of selective transesterification of oil as a function of alcohol, temperature and catalyst concentration was also studied. Although saturated MG’s with high melting points are a greater source of deposits, it can be hypothesized that the polymorphic nature of unsaturated Monoglycerides could also be contributing to cold flow issues. It is hence vital to make sure the biodiesel is free from all forms of monoglycerides. It was also seen that there is very little specificity of selection of fatty acid types in the transesterification reaction and that the amount and type of MGs present in the biodiesel is reflected by the relative amount of fatty acids types present in the oil. In biodiesel derived from Canola oil, a preponderance of monoolein was found for all runs. The initial runs carried out as a two stage process using the membrane followed by batch reactor gave very low MG concentrations, well below ASTM standards.

This work describes the application of porous metal supported Pd-membranes to the water-gas shift catalytic membrane reactor in the context of its potential application to the Integrated Gasification Combined Cycle (IGCC) process. The objective of this work was to develop a better understanding of Pd-membrane fabrication techniques, water-gas shift catalytic membrane reactor operation, and long-term behavior of the Pd-membranes under water-gas shift conditions. Thin (1.5 - 16 um) Pd-membranes were prepared by electroless deposition techniques on porous metal supports by previously developed methods. Pd-membranes were installed into stainless steel modules and utilized for mixed gas separation (H2/inert, H2/H2O, dry syngas, and wet syngas) at 350 - 450C and 14.5 atma to investigate boundary layer mass transfer resistance and surface inhibition. Pd-membranes were also installed into stainless steel modules with iron-chrome oxide catalyst and tested under water-gas shift conditions to investigate membrane reactor operation in the high pressure (5.0 - 14.6 atma) and high temperature (300 - 500C) regime. After the establishment of appropriate operating conditions, long-term testing was conducted to determine the membrane stability through He leak growth analysis and characterization by SEM and XRD. Pd and Pd/Au-alloy membranes were also investigated for their tolerance to 1 - 20 ppmv of H2S in syngas over extended periods at 400C and 14.0 atma. Water-gas shift catalytic membrane reactor operating parameters were investigated with a focus on high pressure conditions such that high H2 recovery was possible without a sweep gas. With regard to the feed composition, it was desirable to operate at a low H2O/CO ratio for higher H2 recovery, but restrained by the potential for coke formation on the membrane surface, which occurred at a H2O/CO ratio lower than 2.6 at 400C. The application of the Pd-membranes resulted in high CO conversion and H2 recovery for the high temperature (400 - 500C) water-gas shift reaction which then enabled high throughput. Operating at high temperature also resulted in higher membrane permeance and less Pd-surface inhibition by CO and H2O. The water-gas shift catalytic membrane reactor was capable of stable CO conversion and H2 recovery (96% and 88% respectively) at 400C over 900 hours of reaction testing, and 2,500 hours of overall testing of the Pd-membrane. When 2 ppmv H2S was introduced into the membrane reactor, a stable CO conversion of 96% and H2 recovery of 78% were observed over 230 hours. Furthermore, a Pd90Au10-membrane was effective for mixed gas separation with up to 20 ppmv H2S present, achieving a stable H2 flux of 7.8 m3/m2-h with a moderate H2 recovery of 44%. The long-term stability under high pressure reaction conditions represents a breakthrough in Pd-membrane utilization.

Biodiesel is rapidly growing as a fuel of interest due to the various advantages it has over conventional diesel fuel. While the pros – non-toxic, biodegradable, low green house gas emissions seem advantageous, the major issue that plagues the use of biodiesel is its cold weather operability. Biodiesel can present challenges in cold-weather operation, because certain of its constituent compounds can form precipitates in the fuel. These precipitates can cause undesired effects like plugging of fuel filters and deposits. This issue has been attributed to the presence of impurities (mostly saturated monoglycerides, di-glycerides, soap etc) in biodiesel and has been discussed in the literature. There is a move by users and standards associations to implement more stringent norms and quality control to avoid problems in the widespread use of biodiesel. This study involves ways to reduce MG’s in biodiesel by mitigating to a greater extent the possibility of side reactions (formation of soap). The effect of selective transesterification of oil as a function of alcohol, temperature and catalyst concentration was also studied. Although saturated MG’s with high melting points are a greater source of deposits, it can be hypothesized that the polymorphic nature of unsaturated Monoglycerides could also be contributing to cold flow issues. It is hence vital to make sure the biodiesel is free from all forms of monoglycerides. It was also seen that there is very little specificity of selection of fatty acid types in the transesterification reaction and that the amount and type of MGs present in the biodiesel is reflected by the relative amount of fatty acids types present in the oil. In biodiesel derived from Canola oil, a preponderance of monoolein was found for all runs. The initial runs carried out as a two stage process using the membrane followed by batch reactor gave very low MG concentrations, well below ASTM standards.

The experiments which are required to directly assess the operational stability of thermostable biocatalysts can be time-consuming, troublesome, and, in the context of industry, expensive. In the present work, we develop and validate two methods for quickly estimating the total turnover number (a useful indicator of lifetime productivity) of a biocatalyst for any desired operating temperature. The first method is a heuristic approach, built upon a complete mathematical derivation from first principles, in which the total turnover number can be calculated from two simple biochemical measurements. The second method relies on a single non-isothermal, continuous-mode experiment in conjunction with mathematical modeling to determine the intrinsic deactivation parameters of the biocatalyst. Both methods provide estimates of the total turnover number which are well within one order of magnitude of the values measured directly via isothermal aging tests and therefore are extremely valuable tools in terms of the amount of experimental time eliminated.

Nanosized metal particles have become an important class of materials in the field of catalysis, optical, electronic, magnetic and biological devices due to the unique physical and chemical properties. This research deals with the synthesis of structured bimetallic nanoparticles for the dechlorination of toxic organics. Nanoparticle synthesis in aqueous phase for dechlorination studies has been reported. However, in the absence of polymers or surfactants particles can easily aggregate into large particles with wide size distribution. In this study, we report a novel in-situ synthesis method of bimetallic nanoparticles embedded in polyacrylic acid (PAA) functionalized microfiltration membranes by chemical reduction of metal ions bound to the carboxylic acid groups. Membrane-based nanoparticle synthesis offers many advantages: reduction of particle loss, prevention of particle agglomeration, application of convective flow, and recapture of dissolved metal ions. The objective of this research is to synthesize and characterize nanostructured bimetallic particles in membranes, understand and quantify the catalytic hydrodechlorination mechanism, and develop a membrane reactor model to predict and simulate reactions under various conditions. In this study, the PAA functionalization was achieved by filling the porous PVDF membranes with acrylic acid and subsequent in-situ free radical polymerization. Target metal cations (iron in this case) were then introduced into the membranes by ion exchange process. Subsequent reduction resulted in the formation of metal nanoparticles (around 30 nm). Bimetallic nanoparticles can be formed by post deposition of secondary appropriate metal such as Pd or Ni. The membranes and bimetallic nanoparticles were characterized by: SEM, TEM, TGA, and FTIR. A specimen-drift-free X-ray energy dispersive spectroscopy (EDS) mapping system was used to determine the two-dimensional element distribution inside the membrane matrix at the nano scale. This high resolution mapping allows for the correlation and understanding the nanoparticle structure, second metal composition in terms of nanoparticle reactivity. Chlorinated aliphatics such as trichloroethylene and conjugated aromatics such as polychlorinated biphenyls (PCBs) were chosen as the model compounds to investigate the catalytic properties of bimetallic nanoparticles and the reaction mechanism and kinetics. Effects of second metal coating, particle size and structure and temperature were studied on the performance of bimetallic system. In order to predict reaction at different conditions, a two-dimensional steady state model was developed to correlate and simulate mass transfer and reaction in the membrane pores under convective flow mode. The 2-D equations were solved by COMSOL (Femlab). The influence of changing parameters such as reactor geometry (i.e. membrane pore size) and Pd coating composition were evaluated by the model and compared well with the experimental data.

Coal gasification is currently being developed as a cleaner alternative to conventional combustion technology. To optimise H2 production in this process, a water gas shift reaction is utilised to convert all CO with H2O to produce CO2 and H2. Typically industrial processes involve a two-step reaction system followed by a downstream H2 purification system, though attracting significant inefficiencies and high capital costs. Replacing a conventional unit process with a membrane reactor in this application is foreseen to provide major advantages: • Removing H2 from the reaction in-situ, a membrane reactor can minimise downstream processing and associated capital and operational costs. • Shift the reaction to higher conversions, improving efficiencies and reducing CO in the outlet. • Provide a purified H2 stream for use in PEM fuel cells, while concentrating the CO2 stream at high pressure for possible sequestration. If the concept of membrane reactor is to be adopted in coal gasification, important material improvements and operational challenges must be overcome before commercialisation can be realised. In addition, the water gas shift reaction has only recently gained interest for membrane reactors and is currently lacking comprehensive research on the effects of operating conditions on both the conversion and separation found within the unit. To this end, these are strong motivations of this work to contribute with knowledge in this field of research. This thesis examines the effects of operating conditions such as temperature, pressure, space velocity, sweep gas rate and feed water ratio on the performance of a water gas shift membrane reactor as compared with a conventional reactor. Novel cobalt silica molecular sieve membranes were used with conventional low temperature water gas shift reaction CuZnAl2O3 catalysts. Two type of membrane reactor configuration were investigated: a small flat template with catalyst on the feed side, and a scale up tube membrane with catalyst placed also in feed stream, the inner shell of the tube membrane. The cobalt silica membranes complied with activated transport, following a flux dependency gas permeation, where He and H2 permeance increased with temperature whilst N2, CO and CO2 showed the opposite effect. Best single gas selectivities were very high, with values of 4500 (He/N2) and 1100 (H2/CO2). In addition, the energy of activation for He and H2 was also very high, in excess of 9-10 kJ.mol-1, clearly indicating the high quality of the membranes employed in this study. It was found that the MR improved CO conversions for a range of space velocities as a function of temperature, which was attributed to both activate transport property of the membrane and increased conversion. Below equilibrium limits this provided an improved H2 production of 5 – 12% at 200-250oC as the removal of H2 through the membrane allowed enhanced conversion. With a set feed rate, the optimum advantage of the MR was seen at a water ratio of 1 as the lower equilibrium limits allowed greater potential for conversion enhancement. With increasing excess water this advantage decreased from 7% down to 0.5% at 300oC. The use of pressure and sweep rate was used to optimise the membranes permeation rate and selectivity. While pressure (or driving force) provided the highest potential for increasing permeation (or flow rate), temperature in tandem with pressure provided the greatest improvement in membrane selectivity, thus increasing H2 concentration from 95 – 99% in the permeate stream. Detailed study of permeate concentrations with changing conditions was undertaken to provide an understanding of the transport properties of silica membranes. It was observed that membrane selectivity and permeation decreased with the gas composition (ie Single>Binary>Ternary). Nevertheless, for separation of a ternary mixture at increased temperatures (250oC) the membrane could provide up to 99% purified H2 while reducing CO down to 700ppm. Competitive gas permeation regimes are an industrial reality which is seldom addressed in membranes for high temperature gas separation. The effect of gas mixtures on permeation and selectivity was attributed to several factors: chemical potential (or driving force) of the feed gas mixture, blockage of micropores by large molecules (CO2 and CO) which in turn affects the percolation of H2. As a result, gas separation was reduced for higher CO and CO2 feed concentrations, leading to a significant reduction in the H2 flow rate. Temperature played a vital role in this competitive process, as H2 diffusivity and CO, CO2 adsorption followed an inverse trend. Thus, increasing temperature led to higher H2 pore diffusivity, while decreasing the competitive effect of CO and CO2 adsorption. The use of cobalt modified silica to improve the hydrothermal stability of the membranes was investigated for use in the water gas shift reaction. It was found that the addition of cobalt stabilised the silica pore network, maintaining microporosity after exposure to steam. This is validated with long term stability testing in a water gas shift membrane reactor, where it was seen that the membrane could provide up to 95% H2 concentration in the permeate for over 200hrs of MR operation. This provided novel work, establishing the feasibility of these membranes for long term testing and operation in an industrial WGS MR.

In this work, inorganic membranes with highly dispersed metallic catalysts on macroporous titania-washcoated alumina supports were produced, characterized and tested in a catalytic membrane reactor. The reactor, operated as a contactor in the forced pore-flow-through mode, was used for the conversion of synthesis gas (H2 + CO) into mixed alcohols and hydrocarbons via the Fischer-Tropsch synthesis. Carbon monoxide conversions of 78% and 90% at near atmospheric pressure (300kPa) and 493K were recorded over cobalt and bimetallic Co-Mn membranes respectively. The membranes also allowed for the conversion of carbon dioxide, thus eliminating the need for a CO2 separation interphase between synthesis gas production and Fischer-Tropsch synthesis. Catalytic tests conducted with the membrane reactor with different operating conditions (of temperature, pressure and feed flow rate) on cobalt-based membranes gave very high selectivity to specific products, mostly higher alcohols (C2 – C8) and paraffins within the gasoline range, thereby making superfluous any further upgrading of products to fuel grade other than simple dehydration. Manganese-promoted cobalt membranes were found not only to give better Fischer-Tropsch activity, but also to promote isomerization of paraffins, which is good for boosting the octane number of the products, with the presence of higher alcohols improving the energy density. The membrane reactor concept also enhanced the ability of cobalt to catalyze synthesis gas conversions, giving an activation energy Ea of 59.5 kJ/mol.K compared with 86.9 – 170 kJ/mol.K recorded in other reactors. Efficient heat transfer was observed because of the open channel morphology of the porous membranes. A simplified mechanism for both alcohol and hydrocarbon production based on hydroxycarbene formation was proposed to explain both the stoichiometric reactions formulated and the observed product distribution pattern.

Biodiesel is rapidly growing as a fuel of interest due to the various advantages it has over conventional diesel fuel. While the pros – non-toxic, biodegradable, low green house gas emissions seem advantageous, the major issue that plagues the use of biodiesel is its cold weather operability. Biodiesel can present challenges in cold-weather operation, because certain of its constituent compounds can form precipitates in the fuel. These precipitates can cause undesired effects like plugging of fuel filters and deposits. This issue has been attributed to the presence of impurities (mostly saturated monoglycerides, di-glycerides, soap etc) in biodiesel and has been discussed in the literature. There is a move by users and standards associations to implement more stringent norms and quality control to avoid problems in the widespread use of biodiesel. This study involves ways to reduce MG’s in biodiesel by mitigating to a greater extent the possibility of side reactions (formation of soap). The effect of selective transesterification of oil as a function of alcohol, temperature and catalyst concentration was also studied. Although saturated MG’s with high melting points are a greater source of deposits, it can be hypothesized that the polymorphic nature of unsaturated Monoglycerides could also be contributing to cold flow issues. It is hence vital to make sure the biodiesel is free from all forms of monoglycerides. It was also seen that there is very little specificity of selection of fatty acid types in the transesterification reaction and that the amount and type of MGs present in the biodiesel is reflected by the relative amount of fatty acids types present in the oil. In biodiesel derived from Canola oil, a preponderance of monoolein was found for all runs. The initial runs carried out as a two stage process using the membrane followed by batch reactor gave very low MG concentrations, well below ASTM standards.

Hydrogen economy is capitalizing the decarbonization of transport and industrial sectors. Ammonia is an attractive intermediate to store and transport hydrogen, due to its low production cost, well developed storage and transportation infrastruc- ture, high hydrogen density in its liquified form (for transportation) and the potential production from renewable energy sources. Although there have been significant ad- vancements in catalyst development for ammonia decomposition, the potential of this technology cannot be fully exploited until significant process development is made. In this sense, catalytic membrane reactors show promising features and performances. In this work, ammonia decomposition has been studied using the following ap- proach: (1) Catalytic Packed Bed Reactor (CPBR) and kinetic modeling, (2) Cat- alytic Packed Bed Membrane Reactor (CPBMR) modeling and (3) CPBMR scale-up. Stage (1) was performed using Ru-K/CaO and Co-Ce catalysts over a wide range of experimental conditions (including pressures up to 16 bar). Stage (2) includes 1-D and 2-D models that were further validated experimentally, also using different software to tackle the stage (3), which aims to give the optimized geometry and properties of a CPBMR for a production of 5 N m3 h−1 of high purity H2 . The results presented in this Thesis enabled to: (1) obtain a reliable kinetic model capable of describing the ammonia decomposition under a wide range of operating conditions, using Ru-K/CaO and Co-Ce catalysts. (2) identify a range of operat- ing conditions where the CPBMR performs better than the CPBR in terms of NH3 conversion, H2 recovery and H2 purity. This range includes: reaction temperature between 250◦C and 500◦C; reaction pressures between 1 and 16 bar; space times be- tween 1 and 15 gcat h mol−1 and H2 permeate pressure higher than the atmospheric pressure (up to 5 bar). (3) scale-up the CPBMR for ammonia decomposition at a pilot scale, encountering that a pilot plant for a production of 5 N m3 h−1 of pure H2 ( >99.99%) could be obtained with a relatively small multitubular arraignment, that might be even smaller than the needed for the same product using other technology.

In this work the synthesis, characterization, and gas transport properties of hydrogen selective silica membranes were studied along with the catalytic reforming of CH₄ with CO₂ (CH₄ + CO z 2 CO + 2 H₂) in a hydrogen separation membrane reactor. The silica membranes were prepared by chemical vapor deposition (CVD) of a thin SiO₂ layer on porous supports (Vycor glass and alumina) using thermal decomposition of tetraethylorthosilicate (TEOS) in an inert atmosphere. These membranes displayed high hydrogen permeances (10⁻⁸ - 10⁷ mol m⁻² s⁻¹ Pa⁻¹) and excellent H₂ selectivities (above 99.9 %) over other gases (CH₄, CO, and CO₂). The membranes were characterized using Scanning Electron Microscopy and Atomic Force Microscopy, and the mechanism of gas transport was studied applying existing theories with a newly developed treatment. The catalytic reforming of CH₄ with CO₂ was carried out in a membrane reactor installed with a hydrogen separation ceramic membrane. The reaction was conducted at various pressures (1 - 20 atm) and temperatures (873 K and 923 K) at non-equilibrium conditions, and the results were compared with those obtained in a packed bed reactor in order to evaluate performance of the membrane reactor for the reaction. It was found that concurrent and selective removal of hydrogen from the reaction in the membrane reactor resulted in considerable enhancements in the yields of the reaction products, H₂ and CO. The enhancements in the product yields in the membrane reactor increased with pressure showing a maximum at 5 atm, and then decreased at higher pressures. This was due to a trade-off between a thermodynamic quantity (hydrogen production by the reaction) and transport property (hydrogen separation through the membrane). It was also found that the reverse water-gas shift (RWGS) reaction occurred simultaneously with the reforming reaction giving the detrimental effect on the reaction system by reducing the amount of hydrogen production in favor of water. This was particularly significant at high pressures. / Ph. D.