Zeolites ZSM-5 (SiO2/Al2O3=30~280) and Y(SiO2/Al2O3=5.2~80) are bound with silica gel (Ludox HS-40 and Ludox AS-40) and alumina (γ- Al2O3 and boehmite) by different binding methods, namely, gel-mixing, powder-mixing and powder-wet-mixing methods. The acidities of the bound catalysts and the zeolite powder are determined by NH3-TPD and FTIR. The textures of these catalysts are analyzed on a BET machine with nitrogen as a probe molecule. The micropore surface area and micropore volume are determined by t-plot method. Micropore volume distribution is determined by Horvath-Kawazoe approach with a cylindrical pore model. Mesopore volume distribution is determined by BJH method from the nitrogen desorption isotherm. Silica from the binder may react with extra-framework alumina in zeolites to form a new protonic acid. SiO2-bound catalysts have less strong acidity, Bronsted acidity and Lewis acidity than the zeolite powder. Also, the strength of strong acid sites of the zeolites is reduced when silica is embedded. Micropore surface area and micropore volume are reduced by about 19% and 18%, respectively, indicating some micropores of ZSM-5 are blocked on binding with silica. SiO2-bound ZSM-5 catalysts have less catalytic activity for butane transformation (cracking and disproportionation) and ethylene oligomerization than ZSM-5 powder. When alumina is used as a binder, both the total acid sites and Lewis acid sites are increased. Micropore surface area and micropore volume of ZSM-5 powder are reduced by 26% and 23%, respectively, indicating some micropores of ZSM-5 are blocked by the alumina binder. Alumina-bound catalysts showed a lower activity for butane transformation and ethylene oligomerization than ZSM-5 powder. Alkaline metals content in the binder is a crucial factor that influences the acidity of a bound catalyst. The metal cations neutralize more selectively Bronsted acid sites than Lewis acid sites. Alkaline metal cations in the binder and micropore blockage cause the bound catalysts to have a lower catalytic activity than the zeolite powder.

Consuming two major greenhouse gases, carbon dioxide (CO2) and methane (CH4), to produce synthesis gas, which is a mixture of carbon monoxide (CO) and hydrogen (H2), CO2 reforming of CH4 shows significant environmental and economic benefits. However, the process has not found wide industrial application due to severe catalyst deactivation, basically caused by carbon formation. Therefore, it is of great interest to develop stable catalysts without severe deactivation. This work is primarily focused on the development of novel nickel-based catalysts to achieve stable operation for CO2 reforming of CH4.<p> Following Dowdens strategy of catalyst design, a series of nickel-based catalysts are designed with a general formula: Ni-Me/AlMgOx (Me = Co, Cu, Fe, or Mn). The designed catalysts are prepared using co-precipitation method and tested for CO2 reforming of CH4. Catalyst screening showed that the Ni-Co/AlMgOx catalyst has superior performance in terms of activity and stability to other Ni-Me/AlMgOx (Me = Cu, Fe, or Mn) catalysts. A 2000 h long-term deactivation test has shown that the Ni-Co/AlMgOx has high activity and excellent stability for CO2 reforming of CH4.<p> Further investigation on the Ni-Co/AlMgOx catalysts shows that adjusting Ni/Co ratio and Ni-Co loading can significantly affect the catalyst performance. Carbon free operation for CO2 reforming of CH4 can be achieved on the catalysts with a Ni/Co close to 1 and Ni-Co overall loading between 4-10 %. In addition, calcination temperature shows important impacts on the performance of Ni-Co/AlMgOx catalysts. A calcination temperature range of 700-900 oC is recommended.<p> The Ni-Co/AlMgOx catalysts are characterized using various techniques such as ICP-MS, BET, CO-chemiosorption, XRD, TPR, TG/DTA, TEM, and XPS. It has been found that the high activity and excellent stability of Ni-Co/AlMgOx catalysts can be ascribed to its high surface area, high metal disperation, small particle size, strong metal-support interaction, and synergy between Ni and Co.<p> Kinetic studies have shown that the CH4 decomposition and CO2 activation could be the rate-determining steps. Both Power-Law and Langmuir-Hinshelwood kinetic models can fit the experiment data with satisfactory results.

<p>The purpose of this work was to design and to develop a high performance catalyst for the production of hydrogen from reforming of crude ethanol and also, to develop the kinetics and reactor model of crude ethanol reforming process. Crude ethanol reforming is an endothermic reaction of ethanol and other oxygenated hydrocarbons such as (lactic acid, glycerol and maltose) with water present in fermentation broth to produce hydrogen (H2) and carbon dioxide (CO2). Ni/Al2O3 catalysts were prepared using different preparation methods such as coprecipitation, precipitation and impregnation methods with different Ni loadings of 10 25 wt.%, 10-20 wt.%, and 10-20 wt.% respectively.</p><p>All catalysts were characterised by thermogravimetric/differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD), (including X-ray line broadening), temperature programmed reduction (TPR), BET surface area measurements, pore volume and pore size distribution analysis. TG/DSC analyses for the uncalcined catalysts showed the catalyst were stable up from 600oC. XRD analyses showed the presence of NiO, NiAl2O4 and Al2O3 species on the calcined catalysts whereas Ni, NiAl2O4, and Al2O3 were present on reduced catalysts. BET surface area decreased and average pore diameter reached a maximum and then decreased as the Ni loading increased. The temperature programmed reduction profiles showed peaks corresponding to the reduction of NiO between 400-600oC and reduction of NiAl2O4 between 700-800oC. Catalyst screening was performed in a micro reactor with calcination temperature, reaction temperature and the ratio of catalyst weight to crude ethanol flow rate (W/Fcrude-C2H5OH) of 600 oC, 400oC and 0.59 h respectively. Maximum crude-ethanol conversion of 85 mol% was observed for catalyst with 15wt% Ni loading prepared by precipitation method (PT15), while maximum hydrogen yield (= 4.33 moles H2 / mol crude-ethanol feed) was observed for catalyst with 15wt% Ni loading prepared by coprecipitation (CP15). </p><p>Performance tests were carried out on (CP15) in which variables such as space velocity (WHSV) 1.68h-1to 4.68h-1, reduction temperature 400 to 600oC and reaction temperature 320 to 520 oC, were changed for optimum performance evaluation of the selected catalyst. The catalyst deactivated over first three hours of 11 hours time-on-stream (TOS) before it stabilized, the reaction conditions resulted in a drop of ethanol conversion from 80 to 70mol%.</p><p>The compounds identified in the liqiud products in all cases were ethanoic acid, butanoic acid, butanal, propanone, propanoic acid, propylene glycol and butanedioic acid. The kinetic analysis was carried out for the rate data obtained for the reforming of crude ethanol reaction that produced only hydrogen and carbon dioxide. These data were fitted to the power law model and Eldey Rideal models for the entire temperature range of 320-520 oC. The activation energy found were 4405 and 4428 kJ/kmol respectively. Also the simulation of reactor model showed that irrespective of the operating temperature, the benefit of an increase in reactor length is limited. It also showed that by neglecting the axial dispersion term in the model the crude ethanol conversion is under predicted. In addition the beneficial effects of W/FAO start to diminish as its value increases (i.e. at lower flow rates).

The main objectives of the present Ph.D. thesis are comprehensive studies on activity, selectivity and stability of iron catalysts supported on carbon nanotubes (CNTs) for Fischer-Tropsch (FT) reactions. In order to prepare iron catalyst supported on CNTs, it was necessary to study CNT synthesis in bulk scale. Therefore, a part of this research was devoted to the production and characterization of CNTs. High purity, aligned films of multi-walled carbon nanotubes were grown on quartz substrates by feeding a solution of ferrocene in toluene, in a carrier gas of Ar/H2, into a horizontal chemical vapour deposition (CVD) reactor. Results for CNTs synthesized using a wide range of toluene concentrations indicated that, for carbon concentrations higher than ~9.6 mol/m3, catalyst deactivation occurs due to encapsulation of iron metal particles.<p> As the first step of catalyst development for FT reactions a fixed bed micro-reactor system was built and the effects of acid treatment on the activity, product selectivity and stability of iron Fischer-Tropsch catalysts supported on carbon nanotubes were studied. The results of Raman analysis showed that the acid treatment increased the number of functional groups as anchoring sites for metal particles. Fe catalysts supported on CNTs which were pre-treated with nitric acid at 110°C were more stable and active compared to the un-treated catalysts. In order to study the effects of catalytic metal site position on FT reactions, a method was developed to control the position of the deposited metal clusters on either the inner or outer surfaces of the CNTs. According to the results of the FT experiments, the catalyst with catalytic metal sites inside the pores exhibited higher selectivity (C₅⁺ = 36 wt%) to heavier hydrocarbons compared to one with sites on the outer surfaces (C₅⁺ = 24 wt%) . In addition, deposition of catalytic sites on the interior surfaces of the nanotubes resulted in a more stable catalyst.<p> The effects of pore diameter and structure of iron catalysts supported on CNTs on Fischer-Tropsch reaction rates and selectivities were also studied. In order to examine the effects of pore diameter, two types of CNTs with similar surface areas and different average pore sizes (12 and 63 nm) were prepared. It was found that the deposition of metal particles on the CNT with narrow pore size (in the range of larger than 10-15 nm) resulted in more active and selective catalyst due to higher degree of reduction and higher metal dispersion.<p> Promotion of the iron catalyst supported on CNTs with Molybdinium in the range of 0.5-1 wt % resulted in a more stable catalyst. Mo improves the stability of the iron catalyst by preventing the metal site agglomeration. Promotion of the iron catalysts with potassium increased the activity of FT and water-gas-shift reactions and the average molecular weight of the hydrocarbon products. Promotion of the iron catalyst supported on CNTs with 0.5% Cu and 1wt% K resulted in an active (5.6 mg HC/g-Fe.h), stable and selective catalyst (C₅⁺ selectivity of 76%) which exhibited higher activity and better selectivity compared to the similar catalysts reported in the literature. Kinetic studies were conducted to evaluate reaction rate parameters using the developed potassium and copper promoted catalyst. It was found that the CO₂ inhibition is not significant for FT reactions. On the other hand, water effects and presence of vacant sites should be considered in the kinetic models. A first-order reaction model verified that the iron catalyst supported on CNTs is more active than precipitated and commercial catalysts. The results of the present Ph.D. thesis research provide a map for designing catalysts using carbon nanotubes as a support. The key messages of the present thesis are as follows:<p> 1- If the interaction of the metal site and support is strong, which poses negative effects on the catalytic performance, carbon nanotubes can be one solution.<p> 2- Acid pre-treatments are required prior to impregnating nanotubes with metal salt solution. Also, the strong acid treatment should be used for deposition of catalytic sites inside the pores of nanotubes.<p> 3- The structure and pore size of nanotubes have significant influence on the stability, activity and selectivity of the target catalyst.<p> 4- The position of the catalytic sites has to be selected based on the type of reaction. In the case of Fischer-Tropsch reactions, the deposition of catalytic sites inside the pores of nanotubes results in higher activity, longer life span.<p> The outcome of this Ph.D. thesis has been published/submitted in the form of 13 journal papers, one patent, one technical report and presented at 11 conferences.

Catalytic supercritical water gasification (SCWG) is a promising technology for hydrogen and methane production from wet organic feedstocks at relatively low temperatures (e.g. <500 oC). However, in order to make this process technically and economically viable, solid catalyst with enhanced activity and improved hydrogen selectivity should be developed. In this study, different aspects of catalytic SCWG have been investigated. The performance of several supported-nickel catalysts were examined to identify catalysts that lead to high carbon conversion and high hydrogen yields under near-critical conditions (i.e. near 374 oC). Moreover, for the first time, the effects of several parameters which dominated the activity of the supported nickel catalysts have been systematically investigated. Among the several different catalyst supports evaluated at 5% nickel loading, α-Al2O3, carbon nanotube (CNT), and MgO supports resulted in highest carbon conversions, while SiO2, Y2O3, hydrotalcite, yttria-stabilized zirconia (YSZ), and TiO2 showed modest activities. Comparing the XRD patterns for the support materials before and after the exposure to supercritical water, α-Al2O3, YSZ, and TiO2 were found to be hydrothermally stable among the metal oxide supports. Using the same amount of nickel on α-Al2O3, the methane yield decreased by increasing the nickel to support ratio whereas the carbon conversion was only slightly affected. At a given nickel to support ratio, a threefold increase in methane yield was observed by increasing the temperature from 350 to 410 oC. The catalytic activity also increased by the addition small quantity of potassium. The activity of Ni/γ-Al2O3 catalyst varied based on the affinity of the catalyst to form nickel aluminate spinel. This is also the first report on the role of oxidative pretreatment of the carbon nanotubes by nitric acid on the performance of these catalysts for the supercritical water gasification process. Using different lignocellulosic feeds, it was found that the gasification of glucose, fructose, cellulose, xylan and pulp resulted in comparable gas yields (± 10%) after 60 min, whereas alkali lignin was substantially harder to gasify. Interestingly, gasification yield of bark, which had a high lignin content, was comparable to those of cellulose. In summary, the Ni/α-Al2O3 catalyst had a higher hydrogen selectivity and comparable catalytic activity to the best commercially available catalysts for SCWG of carbohydrates.

Les reaccions de metàtesi de diens i d'enins catalitzades per espècies carbèniques de ruteni constitueixen poderoses eines àmpliament utilitzades per a la síntesi d'una gran diversitat de productes. La importància de la reacció de metàtesi s'ha posat de manifest amb la concesió del premi Nobel de Química 2005 a Chauvin, Grubbs i Schrock. La recerca de catalitzadors més estables i actius i la preparació de catalitzadors reciclables han merescut els esforços d'un gran nombre de grups durant els últims anys. Grubbs i Hoveyda han introduït carbens N-heterocíclics (NHC) i lligands estirènics quelatants per a la millora dels sistemes catalítics. Una de les estratègies utilitzades per a la recuperació i reciclatge d'aquests sistemes catalítics és l'ancoratge de l'espècie homogènia a un suport polimèric insoluble, sent els polímers orgànics els més comuns. Dins dels inorgànics els treballs són menys nombrosos i corresponen a l'ancoratge a síliques comercials, a sistemes monolítics o a síliques mesoestructurades. La major estabilitat tèrmica, química i mecànica dels polímers inorgànics i les seves elevades àrees superficials els fan alternatives atractives per a la incorporació covalent de lligands orgànics i complexes metàlics. Com a alternativa a l'ancoratge, la part orgànica pot incorporar-se a la matriu inorgànica mitjançant el procés sol-gel. Els híbrids orgànico-inorgànics derivats de sílice obtinguts han experimentat un gran creixement durant la última dècada, amb el desenvolupament de sistemes organitzats en presència de tensioactius. En la present tesi doctoral s'han sintetitzat cinc monòmers diferents de tipus Hoveyda que presenten grups trietoxisilil. El primer és un equivalent del lligand quelatant original de Hoveyda que inclou una cadena espaiadora i un grup trietoxisilil. Altres monòmers són variacions on la cadena espaiadora inclou una urea enlloc d'un carbamat. Un d'ells conté a la seva estructura un grup nitro que ha de potenciar la seva activitat com a catalitzador, mentre que un altre es tracta d'un derivat bisililat, el qual permet la preparació de materials pel procés sol-gel sense que sigui necessària l'addició de tetraetoxisilà (TEOS). A partir dels diferents monòmers s'han sintetitzat materials híbrids orgànico-inorgànics per diversos procediments: procés sol-gel amb diferents quantitats deTEOS i fluorur com a catalitzador, en presència de dodecilamina, que actua com a agent estructurant i com a catalitzador a la vegada i, en el cas del derivat bisililat, també pel procés sol-gel en absència de TEOS. Els mateixos monòmers s'han ancorat a gel de sílice mesoestructurat MCM-41 i a gel de sílice comercial. Tots els materials s'han caracteritzat gràcies a la col·laboració amb el grup de Michel Wong Chi Man de la "Ecole Nationale Superieure de Chimie de Montpellier" mitjançant diferents tècniques: Ressonància magnètica nuclear de silici-29 en estat sòlid (que permet comprovar la unió covalent entre el lligand orgànic i la matriu sililada), mesures d'adorció-desorció de nitrogen pel mètode BET (amb les quals es determina la superfíce específica del material i la distribució dels diàmetres de porus), difracció de raigs X en pols (determinació de la possible estructuració del material), anàlisi elemental (quantitat de matèria orgànica incorporada) i microscopia electrònica de transmissió (TEM). S'observa que els materials presenten superfices específiques majors quan s'han utilitzat agents estructurant i quan la dilució de la part orgànica és major. El tractament dels materials híbrids amb els carbens de Grubbs de primera i/o segona generació ha donat lloc als corresponents catalitzadors suportats. Aquests s'han assajat en reaccions de metàtesi de diens per tal d'obtenir olefines di-, tri- i tetrasubstituides, i també en la metàtesi d'un ení.Dels resultats obtinguts es desprèn que els materials tractats amb el catalitzador de segona generació són els més eficaços i que els catalitzadors heterogènis que provenen de sol-gel són més actius i es reciclen millor que els corresponents a l'ancoratge a MCM-41 o a sílica comercial. En la síntesi de l'1-(4-toluensulfonil)-2,5-dihidro-1H-pirrole s'han realitzat fins a cinc cicles consecutius amb la majoria dels catalitzadors. Aquells materials que contenen el monòmer més semblant al lligand quelatant original de Hoveyda són els que donen una millor capacitat de reciclatge, mentre que els més actius són els que contenen el grup electroatraient nitro. Entre els catalitzadors preparats per sol-gel resulten ser més actius aquells que presenten una major superfície específica i una major dilució del lligand al seu interior. Els materials preparats a partir del monòmer bisililat sense la addició de TEOS presenten, malgrat tenir una superfície nula, una activitat comparable als altament porosos. En la síntesi de l'1-(4-toluensulfonil)-2,5-dihidro-3-metil-1H-pirrole s'han pogut realitzar fins a cinc cicles de catàlisi. Aquests resultats són millors que els descrits a la literatura amb catalitzadors suportats per a aquesta reacció. En la síntesi del 3,4-dimetil-1-(4-toluensulfonil)-2,5-dihidro-1H-pirrole s'han aconseguit realitzar fins a tres cicles amb un dels catalitzadors, i dos amb la majoria. Aquests resultats constitueixen el primer exemple reeixit de preparació d'aquesta olefina tetrasubstituida amb un catalitzador suportat i el primer cas on s'aconsegueix reutilitzar el catalitzador amb un cert èxit. En la metàtesi de l'ení 1-al·liloxi-1,1-difenil-2-propí s'han realitzar fins a cinc cicles amb la majoria dels catalitzadors. Els resultats constitueixen el primer exemple de recuperació d'un catalitzador en una reacció de matàtesi d'enins. / The diene and enyne metathesis reactions catalyzed by ruthenium carbene species are powerful tools widely used by organic chemists for the synthesis of a great diversity of compounds. The great importance of the metathesis reaction has been made clear with the award of the Nobel Prize of Chemistry 2005 to Chauvin, Grubbs and Schrock. In the metathesis field a considerable number of groups in the last years have dedicated their efforts to the search of more stable and active carbene complexes and to the preparation of recoverable catalysts. Grubbs and Hoveyda have introduced N-heterocyclic carbenes (NHC) and chelating styrenic ligands for the improvement of catalytic systems. One of the strategies used for the recovery of the mentioned ruthenium and palladium catalytic systems is the anchorage of the homogeneous species to an insoluble polymeric support, organic polymers being the most commonly used. In the case of inorganic polymers the precedents are scarce and correspond to the anchoring to commercial silicas, monolithic systems or mesostructured silicas. The better thermal, chemical and mechanical stability of inorganic polymers and their high surface areas make them attractive alternatives for the covalent incorporation of organic ligands and metallic complexes. As an alternative to the anchoring method, the organic moiety can be incorporated to the inorganic matrix by the sol-gel process. The silica-based organic-inorganic hybrids obtained by sol-gel have experienced a great boom in the last decade, with the development of organized systems in the presence of surfactants. In this doctoral thesis five Hoveyda-type monomers have been synthesized containing a triethoxysilil group. The first one is equivalent to the original Hoveyda quelating ligand, and includes a spacing chain and a triethoxysilil group. Other monomers have a urea instead of a carbamate as the spacing chain. One of them contains a nitro group which is expected to improve the catalyst activity, whereas another one is a bisililated derivative, which can be used to prepare materials through the sol-gel process without addition of TEOS being necessary. These monomers have been used to prepare organic-inorganic hybrid materials through several strategies: sol-gel process with different TEOS amounts and fluoride as catalyst, dodecilamine acting both as structurating agent and catalyst and, in the case of the bisililated monomer, through the sol-gel process without TEOS being added. The same monomers have been anchored to commercial and to mesostructurated MCM-41 silica gel. All of them have been characterized in collaboration with Michel Wong Chi Man, from the "Ecole Nationale Superieure de Chimie de Montpellier" through several techniques: Solid state 29Si-NMR (in order to verify the covalent bond between the organic moiety and the sililated matrix), BET nitrogen adsorption-desorption measures (specific surface area and pore size distribution of the material) X ray diffraction (possible material structuration), elemental analysis (amount of incorporated organic moiety) and transmission electron microscopy (TEM). Higher surface areas are observed when structurating agents have been used and with the higher dilution of the organic moiety. Treatment of the hybrid materials with Grubbs first and/or second generation carbenes has produced the corresponding supported catalysts. They have been used in diene metathesis reactions leading to di-, tri- and tetrasubstituted olefins, and in an enyne metathesis reaction, too. The results show that the materials treated with the second generation catalyst are the most efficient and that those synthesized by the sol-gel process are more active and more reusable than those obtained by anchoring either to MCM-41 or to commercial silica gel. In the synthesis of 1-(4-toluensulfonyl)-2,5-dihidro-1H-pirrole five consecutive runs have been performed with most of the catalysts. Those materials containing the most similar monomer to the Hoveyda quelating ligand show the best recycling capacity, whereas the more active ones are those with the electron withdrawing nitro group. Among the catalysts prepared by sol-gel, those with higher surface areas and higher dilution of the ligand in the sililated matrix are the more active. The materials prepared with the bisililated monomer without TEOS addition, although having no surface area at all, show a similar activity than the highly porous ones. In the synthesis of 1-(4-toluensulfonyl)-2,5-dihidro-3-methyl-1H-pirrole five consecutive runs have been performed. The results are better than those described in the literature with supported catalysts for this reaction. In the synthesis of 3,4-dimethyl-1-(4-toluensulfonyl)-2,5-dihidro-1H-pirrole three runs have been performed with one of the catalysts, and two with most of the other. These results are the first successful example for the preparation of this tetrasubstituted olefin with a supported catalyst and the first where it has been reused with a certain success. In the metathesis of 1-allyloxi-1,1-diphenyl-2-propyne five runs have been performed with most of the catalysts. The results obtained constitute the first example of recycling of a catalyst in an enyne metathesis reaction.

The ability to effectively remove sulphur from sulphur-poisoned NOx storage/reduction (NSR) catalysts, while minimizing associated fuel penalties and thermal degradation, is important for commercial application of NSR catalysts. As long as sulphur remains in the fuel or lubrication oil formulations, deactivation of NSR catalysts will persist. In an attempt to more fully understand the mechanism of sulphur removal and the associated operating conditions necessary to efficiently decompose sulphates, various gas compositions, temperatures and desulphation methodologies were applied to a commercially supplied catalyst. Experiments were conducted using a pilot scale plug flow catalytic reactor. FTIR spectroscopy and mass spectrometry were used to measure key sulphur species concentrations. Three groups of experiments were conducted. In the first, the effect of gas composition on the amount of sulphur removed from the catalyst was evaluated. In the latter two, high flow cycling desulphation and low flow cycling desulphation were compared. The most effective desulphation gas composition was achieved through the combination of high concentrations of H2, CO and C3H6 and also the inclusion of CO2 and H2O, which released up to 91% of the stored sulphur. The commercial catalyst tested is designed for a dual-leg process. Dual-leg systems are advantageous over single-leg systems in that engine modifications are unnecessary for catalyst regeneration, thereby minimizing losses in vehicle performance. It was found that under conditions appropriate for that application, catalyst desulphation is dominated by the amount of residual surface oxygen. Through the use of short lean phase cycling, to prevent oxygen saturation, the dual-leg application proved effective for sulphate removal, inducing 69% sulphur release compared to 51% when the surface was saturated with oxygen. Multiple stabilities of sulphur exist on the catalyst, which led to residual catalyst sulphates after many desulphations.

The conversion of ethanol to hydrogen or syngas can be achieved by reacting ethanol with water via steam reforming, CH3CH2OH + (1-x)H2O = (4-x)H2 + (2-x)CO + xCO2 (R.1) CH3CH2OH + H2O = 4H2 + 2CO (R.2) CO + H2O = H2 + CO2 (R.3) Ideally, the ethanol steam reforming reaction can achieve a hydrogen yield of 6 moles of hydrogen per mole of ethanol when the value of x in (R.1) equals 2. High theoretical H2 yield makes ethanol steam reforming a very attractive route for H2 production. Thermodynamic equilibrium studies have shown that ethanol steam reforming produces mixtures of H2, CO, CO2, and CH4 below 950 K, while above 950 K the ethanol steam reforming reaction (R.1) adequately describes the product composition In this study a series of 10wt% Ni loaded Mg-Al mixed oxide supported catalysts were evaluated for the production of hydrogen via the steam reforming of ethanol. Mg-Al mixed oxide supported nickel catalysts were found to give superior activity, steam reforming product selectivity (H2 and COx), and improved catalyst stability than the pure oxide supported nickel catalyst at both temperatures investigated. Activity, product selectivity, and catalyst stability were dependent upon the Al and Mg content of the support. At 923 K, the Mg-Al mixed oxide supported nickel catalysts were the best performing catalysts exhibiting the highest steam reforming product yield and were highly stable, showing no signs of deactivation after 20 h of operation. The improved performance of the Mg-Al mixed oxide supported catalysts was related to the incorporation of the pure oxides, MgO and Al2O3, into MgAl2O4. The formation of MgAl2O4 reduced nickel incorporation with the support material since MgAl2O4 does not react with Ni; therefore, nickel was retained in its active form. In addition, incorporation of Mg and Al in to MgAl2O4, a slight basic material, modified the acid-base properties resulting in a catalyst that exhibited moderate acidic and basic site strength and density compared to the pure oxide supported catalysts. Moderation of the acid-base properties improved the activity, selectivity, and stability of the catalysts by reducing activity for by-product reactions producing ethylene and acetaldehyde. At lower reaction temperatures, below 823 K, Mg-Al mixed oxide supported nickel catalysts experienced substantial deactivation resulting in reduced ethanol conversion but interestingly, the H2 and CO2 yields increased, exceeding equilibrium expectations with time on stream while CH4 yield decreased far below equilibrium expectations, suggesting a direct ethanol steam reforming reaction pathway. Over stabilized Mg-Al mixed oxide supported nickel catalysts, direct ethanol steam reforming was activated by a reduction in the catalyst’s activity for the production and desorption of CH4 from the surface. The effect of pressure on the direct ethanol steam reforming reaction pathway over stabilized Mg-Al mixed oxide supported nickel catalysts was investigated at 673 and 823 K. At 823 K, increasing the total pressure resulted in a product distribution that closely matched the thermodynamic expectations. However, at 673 K, the product distribution deviated from thermodynamic expectations, giving substantially greater yields for the steam reforming products, H2, CO, and CO2, while CH4 yield was consistently less than equilibrium expectations. The identification of an alternative direct ethanol steam reforming reaction pathway at relatively low temperatures (below 823 K) that could be operated at elevated pressures will result in an energy efficient process for the production of hydrogen from bio-ethanol.

With steadily increasing emissions regulations being imposed by government agencies, automobile manufacturers have been developing technologies to mitigate NOX emissions. Furthermore, there has been increasing focus on CO2 emissions. An effective approach for CO2 reduction is using lean burn engines, such as the diesel engine. An inherent problem with lean-burn engine operation is that NOX needs to be reduced to N2, but there is an excess of O2 present. NOX storage and reduction (NSR) is a promising technology to address this problem. This technology operates in two phases; where in the lean phase, normal engine operation, NOX species are stored as nitrates, and in a reductant rich phase, relative to O2, the NOx storage components are cleaned and the NOX species reduced to N2. In this study, the effects of reductant type, specifically CO and/or H2, and their amounts as a function of temperature on the trapping and reduction of NOX over a commercial NSR catalyst have been evaluated. Overall, the performance of the catalyst improved with each incremental increase in H2 concentration. CO was found ineffective at 200°C due to precious metal site poisoning. The addition of the H2 to CO-containing mixtures resulted in improved performance at 200°C, but the presence of the CO still resulted in decreased performance in comparison to activity when just H2 was used. At 300-500°C, H2, CO, and mixtures of the two were comparable for trapping and reduction of NOX, although the mixtures led to slightly improved performance. Although NSR technology is very efficient in reducing NOX emissions, a significant challenge that questions their long-term durability is poisoning by sulfur compounds inherently present in the exhaust. Therefore, during operation, NSR catalysts require an intermittent high-temperature exposure to a reducing environment to purge the sulfur compounds from the catalyst. This desulfation protocol ultimately results in thermal degradation of the catalyst. As a second phase of this study, the effect of thermal degradation on the performance of NSR technology was evaluated. The catalyst performance between a 200 to 500°C temperature range, using H2, CO, and a mixture of both H2 and CO as reductants was tested before and after different high-temperature aging steps. Tests included water-gas shift (WGS) reaction extent, NO oxidation, NOX storage capacity, oxygen storage capacity (OSC), and NOX reduction efficiency during cycling. The WGS reaction extent was affected by thermal degradation, but only at low temperature. NO oxidation did not show a consistent trend as a function of thermal degradation. The total NOX storage capacity was tested at 200, 350 and 500°C. Little change was observed at 500°C with thermal degradation and a steady decrease was observed at 350°C. At 200°C, there was also a steady decrease of NOX storage capacity, except after aging at 700°C, where the capacity increased. There was also a steady decrease in oxygen storage capacity at test temperatures between 200 and 500°C after each increase in thermal degradation temperature, except again when the sample was degraded at 700°C, where an increase was observed. In the cycling experiments, a gradual drop in NOX conversion was observed after each thermal degradation temperature, but when the catalyst was aged at 700°C, an increase in NOX conversion was observed. These data suggest that there was redispersion of a trapping material component during the 700°C thermal degradation treatment while the oxygen storage capacity data indicate redispersion of oxygen storage components. It therefore seems likely that it is these oxygen storage components that are becoming ‘‘activated’’ as trapping materials at low temperature.

The ability to effectively remove sulphur from sulphur-poisoned NOx storage/reduction (NSR) catalysts, while minimizing associated fuel penalties and thermal degradation, is important for commercial application of NSR catalysts. As long as sulphur remains in the fuel or lubrication oil formulations, deactivation of NSR catalysts will persist. In an attempt to more fully understand the mechanism of sulphur removal and the associated operating conditions necessary to efficiently decompose sulphates, various gas compositions, temperatures and desulphation methodologies were applied to a commercially supplied catalyst. Experiments were conducted using a pilot scale plug flow catalytic reactor. FTIR spectroscopy and mass spectrometry were used to measure key sulphur species concentrations. Three groups of experiments were conducted. In the first, the effect of gas composition on the amount of sulphur removed from the catalyst was evaluated. In the latter two, high flow cycling desulphation and low flow cycling desulphation were compared. The most effective desulphation gas composition was achieved through the combination of high concentrations of H2, CO and C3H6 and also the inclusion of CO2 and H2O, which released up to 91% of the stored sulphur. The commercial catalyst tested is designed for a dual-leg process. Dual-leg systems are advantageous over single-leg systems in that engine modifications are unnecessary for catalyst regeneration, thereby minimizing losses in vehicle performance. It was found that under conditions appropriate for that application, catalyst desulphation is dominated by the amount of residual surface oxygen. Through the use of short lean phase cycling, to prevent oxygen saturation, the dual-leg application proved effective for sulphate removal, inducing 69% sulphur release compared to 51% when the surface was saturated with oxygen. Multiple stabilities of sulphur exist on the catalyst, which led to residual catalyst sulphates after many desulphations.