Fischer-Tropsch synthesis is the technology for converting fuel feedstocks such as natural gas and coal into transportation fuels and heavy hydrocarbons. There is scope for research and development into integrated processes utilising synthesis gas for the production of a wide range of hydrocarbons. For this purpose there should be strategies for the development of Fischer-Tropsch processes, which consider both economic and technological feasibilities. The aim of this study was to optimize Fischer Tropsch Plants in order to produce gasoline and gas oil by investigating the benefits of recycling & co-feeding of unconverted gas, undesired compounds, and lighter hydrocarbons over iron-based catalysts in order to save on capital and operating costs. This involved development of FT models for both two-phase and three-phase reactors. The kinetic parameters for these models were estimated using optimization with MATLAB fitting to experimental data and these models were then applied to ASPEN HYSYS flowsheets in order to simulate nine different Fischer-Tropsch plant designs. The methodology employed involved qualitative modelling using Driving Force Analysis (DFA) which indicates the necessity of each compound for the Fischer-Tropsch reactions and mechanism. This also predicts each compounds influence on the selectivity of different products for both two-phase and three-phase reactors and for both pure feeding and co-feeding arrangements. In addition, the kinetic models for both two-phase and three-phase reactor were modified to account for parameters such as the size of catalyst particles, reactor diameter and the type of active sites used on the catalyst in order to understand and quantify their effects. The kinetic models developed can describe the hydrocarbon distributions consistently and accurately over large ranges of reaction conditions (480-710K, 0.5-2.5MPa, and H2/CO ratio: 0.5-2.5) over an iron-based catalyst for once-through processes. The effect of recycling and co-feeding on the iron-based catalyst was also investigated in the two reactor types. It was found that co-feeding unwanted compounds to synthesis gas increases the production of hydrocarbons. This recycling and co-feeding led to an increase in H2/CO feed ratio and increased selectivity towards C5+ products in addition to a slightly increased production of light hydrocarbons (C1-C4). Finally, the qualitative model is compared with the quantitative models for both two-phase and three-phase reactors and using both pure feeding and co-feeding with the same reactor conditions. According to the detailed quantitative models developed, in order to maximize hydrocarbon production pressures of 2MPa, temperatures of 450K and a H2/CO feed ratio of 2:1 are required. The ten different Fischer-Tropsch plant cases were based on Fischer-Tropsch process. FT reactor models were built in ASPEN HYSYS and validated with real FT plant data. The results of the simulation and optimization supported the proposed process plant changes suggested by qualitative analysis of the different components influence. The plants involving recycling and co-feeding were found to produce higher quantities of gasoline and gas oil. The proposed heuristic regarding the economic scale of the optimized model was also evaluated and the capital cost of the optimized FT plant reduced comparison with the real FT plant proposed by Gerard. Therefore, the recycling and co-feeding to FT reactor plant was the best efficiency to produce both gasoline and gas oil.

This research project is part of a larger Canadian endeavour to evaluate feasibility of using new nanocatalyst formulations for Fischer-Tropsch synthesis (FTS) to convert fossil-derived or renewable gaseous fuels into green diesel. The green diesel is a clean fuel (with no aromatics and sulfur compounds) suitable for the commonly used transportation system. The catalyst investigated is cobalt metal supported on carbon nanotubes (CNTs). The physical properties of CNTs have improved the common cobalt catalyst currently used in industry. Carbon nanotubes have high surface area, a very stable for FTS activity and, contrary to other common supports, do not interact with the catalyst active phase to produce undesirable compounds. Moreover, CNTs differ from graphite in their purity and by their cylindrical form, which increases the metal dispersion and allows confinement of the particles inside the tubes. Thus, carbon nanotubes as a new type of carbon material have shown interesting properties, favoring catalytic activity for FTS cobalt catalyst. Their surface area can be modified from 170 to 214 m^2/g through acid treatment. The CNT support lowers the amount of Ru promoter needed to increase the catalyst activity up to 80 % CO conversion and potassium promoter increases the selectivity for á-olefins. The olefin to paraffin (O/P) ratio for Co/CNT and CoK/CNT are 0.76 and 0.90, respectively. Moreover, the Co-Fe bimetallic catalysts supported on CNT have proved to be much more attractive in terms of alcohol formation, up to 26.3 % for the Co10Fe4/CNT. The structural characteristics of CNTs have shown to be suitable for use as catalytic support materials for FTS using microemulsion preparation method as applied to produce nanoparticle catalysts. Microemulsion technique results show uniform nanoparticle that are easy to reduce. In addition, the confinement of the particles inside the CNT has improved the lifetime of the catalyst by decreasing the rate of sintering. The deactivation rate at high FTS activity is linear (XCO = -0.13 t(hr) + 75) and at low FTS activity is related to a power law expression of order 11.4 for the cobalt particles outside the tubes and 30.2 for the cobalt particles inside the tube. The optimized catalyst studied was the CoRuK/CNT catalyst. The best kinetic model to describe the CoRuK/CNT catalyst is: 18.5 x 10 ^-5 PH2^0.39/ (1 + 7.2 10 ^-2 PCO^0.72 PH2^0.1)^2.

This research project is part of a larger Canadian endeavour to evaluate feasibility of using new nanocatalyst formulations for Fischer-Tropsch synthesis (FTS) to convert fossil-derived or renewable gaseous fuels into green diesel. The green diesel is a clean fuel (with no aromatics and sulfur compounds) suitable for the commonly used transportation system. The catalyst investigated is cobalt metal supported on carbon nanotubes (CNTs). The physical properties of CNTs have improved the common cobalt catalyst currently used in industry. Carbon nanotubes have high surface area, a very stable for FTS activity and, contrary to other common supports, do not interact with the catalyst active phase to produce undesirable compounds. Moreover, CNTs differ from graphite in their purity and by their cylindrical form, which increases the metal dispersion and allows confinement of the particles inside the tubes. Thus, carbon nanotubes as a new type of carbon material have shown interesting properties, favoring catalytic activity for FTS cobalt catalyst. Their surface area can be modified from 170 to 214 m^2/g through acid treatment. The CNT support lowers the amount of Ru promoter needed to increase the catalyst activity up to 80 % CO conversion and potassium promoter increases the selectivity for á-olefins. The olefin to paraffin (O/P) ratio for Co/CNT and CoK/CNT are 0.76 and 0.90, respectively. Moreover, the Co-Fe bimetallic catalysts supported on CNT have proved to be much more attractive in terms of alcohol formation, up to 26.3 % for the Co10Fe4/CNT. The structural characteristics of CNTs have shown to be suitable for use as catalytic support materials for FTS using microemulsion preparation method as applied to produce nanoparticle catalysts. Microemulsion technique results show uniform nanoparticle that are easy to reduce. In addition, the confinement of the particles inside the CNT has improved the lifetime of the catalyst by decreasing the rate of sintering. The deactivation rate at high FTS activity is linear (XCO = -0.13 t(hr) + 75) and at low FTS activity is related to a power law expression of order 11.4 for the cobalt particles outside the tubes and 30.2 for the cobalt particles inside the tube. The optimized catalyst studied was the CoRuK/CNT catalyst. The best kinetic model to describe the CoRuK/CNT catalyst is: 18.5 x 10 ^-5 PH2^0.39/ (1 + 7.2 10 ^-2 PCO^0.72 PH2^0.1)^2.

Several self-supported and metal oxide supported cobalt Fisher-Tropsch (FT) catalysts were prepared applying incipient wetness impregnation method. The catalysts were characterized by TPR, adsorption-desorption, XRD, TEM and SEM. The gas products were characterized by GC. The effect of support was investigated. The selfsupported 3D ordered macro-porous (3DOM) Fe-Co and self-supported 2D ordered mesoporous catalyst showed low or no activity under typical F-T reaction conditions. The 3DOM Al2O3 supported cobalt catalyst showed much higher CO conversion and C4+ selectivity than conventional Co/Gamma-Al2O3 catalyst. However, the 3DOM Co/Al2O3 prepared by incorporated method showed no activity. The supported Co/SBA-15 performed better CO conversion than the conventional Co/SiO2. The effects of temperature and time on 3DOM Co/Al2O3 and Co/SBA-15 system were coherent with traditional catalysts. The well-defined structure of 3DOM Al2O3 and SBA-15 may favor to the selectivity of C4+ hydrocarbons product.

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.

La presente tesis doctoral está centrada en la investigación de los parámetros estructurales que determinan las propiedades catalíticas en la síntesis de Fischer-Tropsch (SFT) de catalizadores de cobalto soportados en TiO2. Por un lado, el estudio de la influencia del polimorfo de óxido de titanio (rutilo vs. anatasa) utilizado como soporte en catalizadores de Co promovidos con Ru ha permitido obtener correlaciones entre la estructura cristalina del soporte, la extensión del efecto SMSI (interacción fuerte metal-soporte) y los resultados catalíticos. Por otro lado, mediante la modificación de las propiedades texturales del soporte TiO2-anatasa con el objetivo de obtener catalizadores con baja, media y alta área superficial se ha podido avanzar en el conocimiento del efecto SMSI y su correlación con las propiedades texturales del soporte. Además, las consecuencias del aumento en área superficial del soporte en la actividad y selectividad de catalizadores CoRu/TiO2 para la SFT se han podido explicar en base a las relaciones establecidas entre estructura y efecto SMSI. Adicionalmente, el uso de técnicas de luz sincrotrón junto con caracterización espectroscópica in situ realizada a presiones superiores a la atmosférica, ha permitido explicar el papel de la adición y concentración de Ru como promotor en catalizadores CoRu/TiO2. Finalmente, se han estudiado tratamientos de reducción-oxidación-reducción (ROR) en catalizadores CoRu/TiO2 con el objetivo de mejorar su actividad catalítica. Como conclusión general, los conocimientos derivados de los resultados obtenidos en esta tesis doctoral pueden aportar estrategias adecuadas para el diseño de catalizadores de FT mejorados basados en Co empleando TiO2 como soporte. / The present doctoral thesis focused on the investigation of the structural parameters that can determine the ultimate catalytic properties for Fischer-Tropsch synthesis (FTS) of TiO2-supported cobalt catalysts. On the one hand, the study of the influence of the titania polymorph (rutile vs. anatase) as support for Ru-promoted Co and Ru nanoparticles (NPs) has allowed to identify some correlations between the TiO2 crystalline phase, the SMSI (strong metal-support interaction) effect, and the catalytic performance for FTS of the catalysts. On the other hand, by preparing CoRu catalysts supported on TiO2-anatase with low, medium, and high surface area, further insights into the SMSI effect and its dependence on the textural properties of the TiO2-anatase support have been gained. Besides, the consequences of increasing the surface area of the support on the activity and selectivity of the catalysts for FTS have been explained based on the established structure-SMSI relationships. Moreover, a detailed study involving the use of in situ synchrotron-based spectroscopic characterizations at pressures higher than the ambient pressure usually applied in most previous works, has been carried out aiming at explaining the role of Ru addition and concentration as promoter in Co/TiO2 catalysts. Finally, reduction-oxidation-reduction (ROR) treatments have been applied on CoRu/TiO2 catalysts to revert the SMSI effect as a feasible strategy to enhance their catalytic activity. Overall, the results reported in this thesis provide grounds for designing TiO2-supported Co catalysts with improved activity and selectivity for FTS. / La present tesi doctoral està centrada en la investigació dels paràmetres estructurals que poden tenir influència en les propietats catalítiques dels catalitzadors que s'han aplicat a la reacció de síntesi de Fischer-Tropsch (SFT). S'ha estudiat la influència del polimorf de titani (rutil o anatasa) utilitzat com a suport de nanopartícules (NPs) de Co i Ru, observant correlacions entre l'estructura cristal·lina del suport, l'efecte SMSI (forta interacció metall-suport) i els resultats catalítics. D'altra banda, es va fer un estudi modificant les propietats texturals de la anatasa amb l'objectiu d'obtenir catalitzadors amb diferent àrea superficial, i s'ha pogut establir un coneixement més profund de l'efecte SMSI i la seua correlació amb les propietats texturals del suport. A més, la influència de l'augment de l'àrea superficial del suport per a la reacció de SFT, en termes d'activitat i selectivitat, han sigut explicats d'acord a les relacions establides entre l'estructura i l'efecte SMSI. Addicionalment, fent ús de tècniques de llum sincrotró juntament amb caracterització in situ realitzada a altes pressions, ha sigut possible explicar el paper de l'addició i concentració de Ru com a promotor en catalitzadors CoRu/TiO2. Finalment, s'han estudiat els tractaments de reducció-oxidació-reducció (ROR) en catalitzadors CoRu/TiO2 amb l'objectiu de millorar la seua activitat catalítica. En resum, els coneixements derivats dels resultats obtinguts en esta tesi doctoral permeten establir estratègies per al disseny de catalitzadors millorats per a la síntesi de FT basats en cobalt utilitzant TiO2 com a suport. / Bertella, F. (2018). Structural, promotion and metal-support interaction effects in Co/TiO2 catalysts for Fischer-Tropsch synthesis [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/107952 / TESIS

A potential route for converting different carbon sources (coal, natural gas and biomass) into synthetic fuels is the transformation of these raw materials into synthesis gas (CO and H2), followed by a catalytic step which converts this gas into the desired fuels. The present thesis has focused on two catalytic steps: Fischer-Tropsch synthesis (FTS) and methanation. The Fischer-Tropsch synthesis serves to convert synthesis gas into liquid hydrocarbon-based fuels. Methanation serves instead to produce synthetic natural gas (SNG). Cobalt catalysts have been used in FTS while nickel catalysts have been used in methanation.             The catalyst lifetime is a parameter of critical importance both in FTS and methanation. The aim of this thesis was to investigate the deactivation causes of the cobalt and nickel catalysts in their respective reactions.             The resistance to carbonyl-induced sintering of nickel catalysts supported on different carriers (γ-Al2O3, SiO2, TiO2 and α-Al2O3) was studied. TiO2-supported nickel catalysts exhibited lower sintering rates than the other catalysts. The effect of the catalyst pellet size was also evaluated on γ-Al2O3-supported nickel catalysts. The use of large catalyst pellets gave considerably lower sintering rates. The resistance to carbon formation on the above-mentioned supported nickel catalysts was also evaluated. Once again, TiO2-supported nickel catalysts exhibited the lowest carbon formation rates. Finally, the effect of operating conditions on carbon formation and deactivation was studied using Ni/TiO2 catalysts. The use of higher H2/CO ratios and higher pressures reduced the carbon formation rate. Increasing the temperature from 280 °C to 340 °C favored carbon deposition. The addition of steam also reduced the carbon formation rate but accelerated catalyst deactivation.             The decline in activity of cobalt catalysts with increasing sulfur concentration was also assessed by ex situ poisoning of a cobalt catalyst. A deactivation model was proposed to predict the decline in activity as function of the sulfur coverage and the sulfur-to-cobalt active site ratio. The results also indicate that sulfur decreases the selectivity to long-chain hydrocarbons and olefins. / <p>QC 20160817</p>

The use of biomass as a potential feedstock for the production of liquid hydrocarbon fuels has been under investigation in the last few decades. This paper discusses a preliminary design and a feasibility study of producing liquid hydrocarbon fuels from biomass through a combined biochemical and thermochemical route. The process involves anaerobic digestion (AD) of the biodegradable portion of the biomass to produce methane rich gas. The methane rich biogas stream is purified by removing contaminants and upgraded to liquid hydrocarbon fuel in a gas to liquid facility (GTL) via thermochemical conversion route. The biogas conversion involves two major steps: tri-reforming step to produce syngas (a mixture of CO and H2), and Fischer-Tropsch Synthesis (FTS) step to convert the syngas to a spectrum of hydrocarbons. Separation and upgrading of the produced hydrocarbon mixture allows production of synthetic transportation fuels. AD is ranked as one of the best waste management options as it allows for: energy recovery, nutrient recovery, and reduction in greenhouse gases emission. A detailed process modeling of the process was carried out using ASPEN Plus process design software package. Data for the process was based on literature on AD combined with laboratory results on the biogas to liquid conversion process. The composition of the final liquid hydrocarbon from the ASPEN model has been compared to the composition of commercial diesel fuel, and results have shown good agreement. As a result, the most current commercial diesel prices were used to evaluate the potential revenue from selling the product in the open market. The total capital investment to construct the plant with a capacity of handling 100,000 ton per year of wet biomass is $16.2 million with a potential of producing 2.60 million gallons of diesel. The base case feedstock is corn stover. The annual operating cost to run the plant is estimated to be $8.81 million. An annual revenue from selling the diesel product is estimated to be $14.6 million taking into account a green energy incentive of $3.00/gallon of diesel sold. The net present worth at the end of the plant life is $8.76 million with a discounted cash flow of return of 26.2%. The breakeven cost of diesel is determined to be $4.34/gallon assuming no tipping fees are charged for handling the waste. Sensitivity analyses results concluded that the profitability of the process is most sensitive to variation in diesel selling price. Based on these results, it can be concluded that the process is profitable only if incentives are provided for renewable fuels due to the current low prices of fossil fuels.

CO hydrogenation and CO oxidation are two important processes addressing the energy and environmental issues of great interest. Both processes are carried out using metallic catalysts. The objective of this dissertation is to study the catalytic processes that govern these two reactions from a molecular perspective using quantum mechanical calculations. Density Functional Theory (DFT) has proven to be a valuable tool to study adsorption, dissociation, chain growth, reaction pathways etc., on well-defined surfaces. DFT was used to study the CO reduction reactions on promoted cobalt catalyst surfaces and CO oxidation mechanisms on cobalt surfaces. CO hydrogenation via Fischer-Tropsch Synthesis (FTS) is a process used to produce liquid fuels from synthesis gas. The economics of the Fischer-Tropsch process strongly depends on the performance of the catalyst used. The desired properties of a catalyst include selectivity towards middle distillate products such as diesel and jet fuel, higher activity and longer catalyst life. Catalysts are often modified by adding promoters to obtain these desirable properties. Promoters can influence the reaction pathways, reducibility, dispersion, activity and selectivity. In FTS, understanding the effect of promoters in the molecular scale would help in tailoring catalysts with higher activity and desired selectivity. Preventing deactivation of catalyst is important in FTS to increase the catalyst life. Deactivation of Co catalyst can occur by reoxidation, C deposition, sintering, formation of cobalt-support compounds etc. Designing catalyst with resistance to deactivation by the use of promoters is explored in this dissertation. The influence of promoters on the initiation pathways of CO hydrogenation is also explored as a first step towards determining the selectivity of promoted catalyst. The influence of Pt promoter on O removal from the surface of Co catalyst showed that Pt promoter reduced the activation barrier for the removal of O on both flat and stepped Co surfaces. An approximate kinetic model was developed and a volcano plot was established. The turn-over frequency (TOF) calculated based on the activation barriers showed that Pt promoted Co surface had a higher rate than unpromoted Co surface. The effect of Pt and Ru promoters on various pathways of C deposition on Co catalyst was studied to gain a mechanistic understanding. The promoters did not affect the subsurface C formation but they increased the barriers for C-C and C-C-C formation and also decreased the barriers for C-H formation. The promoters also influence the stabilities of C compounds on the Co surface suggesting that Pt and Ru promoters would decrease C deposition on Co catalysts. The effect of Pt promoter on unassisted and H-assisted CO activation pathways on Co catalyst was studied. Pt promoted Co surface followed H-assisted CO activation. Pt promoter decreased the activation barriers for CO activation pathways on Co catalyst thereby increasing the activity of Co catalyst. CO oxidation is a process used to prevent poisoning of fuel cell catalysts and reduce pollution of the atmosphere through exhaust gases containing CO. Expensive catalysts like Pt are widely used for CO oxidation which significantly increases the cost of the process and hence it is necessary to search for alternative lower cost catalysts. Understanding the mechanism of a reaction is the first step towards designing better and efficient catalyst. DFT is helpful in determining the basic mechanism and intermediates of reactions. The mechanism of CO oxidation on CoO catalyst was explored. Four possible mechanisms for CO oxidation on CoO catalyst were studied to determine the most likely mechanism. The mechanism was found to be a two-step process with activation barrier for formation of CO2 larger than the barrier for formation of the intermediate species.

As hydrogen is increasingly used as an energy carrier, gas sensors that can operate at high temperatures and in harsh environments are needed for fuel cell, aerospace, and automotive applications. The high temperature Fischer-Tropsch process also uses mixtures of hydrogen and carbon monoxide to generate synthetic fuels from non-fossil precursors. As the Fischer-Tropsch process depends upon particular gas mixtures to generate various fuels, a sensor which can determine the proper ratio of reactants is needed. To this end, gallium nitride (GaN) has been used to fabricate a resistive gas sensor. GaN is a suitable semiconductor to be used in hydrogen because of a wide, direct bandgap and greater stability than many other semiconductors. Additionally, resistive sensors offer several advantages in design compared to other types of sensors. Response time of resistive sensors is faster than those of other semiconductor sensors because catalytic and diffusion steps are not part of the response mechanism. Instead, a thermal detection mechanism is employed in resistive sensors. In this work, sensor response to changes in hydrogen concentration in nitrogen was measured at 200°C and 300°C. Sensor response was measured as change in current from a reference response to pure nitrogen at each temperature under a constant 2.5 V bias. Isothermal operation was achieved by controlling sensor temperature and pre-heating gas mixtures. Sensitivity to concentration increased upon an increase in temperature. Additionally, sensor response to concentration changes of H2 in CO at 50 °C was demonstrated. Sensors show similar responses to nitrogen and carbon monoxide mixtures, which have similar thermal properties. Using the thermal detection mechanism of the sensors, a correlation was shown between sensor response and a gas mixture thermal conductivity.