This paper presents the culmination of an investigation on carbon nanotubes as catalysts for the hydrogenation of carbon monoxide. Carbon nanotubes (CNTs) have been found to have extraordinary physical properties and the potential for use in a variety of applications. They have been utilized as catalyst supports in many reactions, including the conversion of syngas to ethanol. The specific role played by CNTs in these reactions, aside from that of a support structure, has not been evaluated, however. Presented here are parametric studies on Fischer-Tropsch Synthesis with carbon nanotubes as active catalysts. The use of as-produced CNTs (containing trace amounts of iron from the synthesis process) resulted in a 100-fold increase in carbon monoxide conversion per unit mass of catalyst over a traditional Fe-Zn-K/γ-alumina catalyst. This value (CO conversion per unit mass of catalyst) was raised to nearly 1500 times as high as for Fe-Zn-K/γ-alumina when purified CNTs were used in the same FT synthesis. Because iron is a primary catalyst in the FT synthesis, it can be argued that the iron in the CNTs was responsible for the catalytic behavior. However, the iron content in the MWNTs (0.014 g, ≈ 5 mass%) and SWNTs (0.04 g, ≈ 27 mass%) compared to that of the traditional iron-loaded alumina support (2.5 g, ≈ 12.5 mass%), strongly suggests that iron alone cannot be responsible for the catalysis. Although single-walled nanotube (SWNT) catalysts provided high CO conversion, methane represented the bulk of the products. Conversely, multi-walled nanotubes (MWNTs) produced mostly liquid hydrocarbons and oxygenates, indicating that the CNT structure is an important factor in the hydrogenation of CO. The parametric experiments show that temperature, pressure and the syngas composition all play key roles in the distribution of liquid products. In general, an increase in temperature correlated to an increase in hydrocarbon chain length and the formation of more alcohols; above a certain temperature, the distribution shifted to 100% alcohols. Likewise, lower pressures resulted in hydrocarbons of shorter carbon chain length and at higher pressures, more alcohols were formed. Studies were also conducted on the effect of syngas composition and the effect of different types of CNTs. Syngas with 1:1 ratio (H2:CO) produced longer hydrocarbon chains than those produced by 3:1 syngas. The type of CNTs used in FT also affected the products but no clear relationships could be discerned.

A descoberta de uma nova província petrolífera, conhecida como pré-sal, localizada no litoral brasileiro, representa um novo marco na produção de petróleo mundial. Dentre os vários desafios encontrados para exploração e produção dessa região, a presença de CO2 em grandes concentrações nos fluidos de alguns desses reservatórios tem sido um dos desafios de maior relevância para as empresas que exploram e produzem nessa área (FORMIGLI, 2007). Uma forma alternativa de sequestro do CO2 retirado do gás natural é a sua utilização como matéria prima ou co-alimentação para a síntese de produtos químicos, em especial aqueles com grande demanda de mercado. Um dos produtos que podem ser obtidos indiretamente a partir do CO2 é o petróleo sintético, produzido pelo processo conhecido como Gas-to-Liquids, ou GTL. Neste trabalho foi analisada a viabilidade técnica, econômica e potencial de captura de CO2, da produção de petróleo sintético, pelo processo GTL, offshore, a partir de dióxido de carbono (CO2) e metano (CH4), presentes na corrente de rejeito do tratamento do gás processado em uma plataforma de produção de petróleo e gás, através das reformas seca e a vapor, seguida da síntese Fischer-Tropsch. A partir de dados de literatura e com uso de simulador comercial de processos, a simulação do processo foi desenvolvida e diferentes alternativas para reaproveitamento das correntes residuais do processo foram analisadas, incluindo o reciclo e a queima dos efluentes combustíveis, assim como foram aplicadas técnicas de integração energética, otimização e análise econômica de processos. Os resultados indicaram que o processo, mássica e energeticamente integrado, na condição de menor emissão de CO2 e maior retorno financeiro, produziu petróleo sintético de forma técnica e economicamente viável. Os resultados indicaram ainda que o processo GTL, com as tecnologias utilizadas, não é indicado como método de captura de CO2 devido o fato de a geração desse componente para a produção de petróleo sintético ser duas vezes maior que a quantidade alimentada. / The discovery of a new oil province known as pre-salt, located in the Brazilian coast, represents a new frontier in the world\'s oil production. Among other challenges involved in the exploration and production in that region, the CO2 concentration at high levels in the fluids of some of those reservoirs has been the most relevant challenge for the companies that explore and produce in that area (FORMIGLI, 2007). An alternative to sequestering the CO2 extracted from natural gas is using it as a supply of raw material or as an input to the synthesis of chemical products, especially those with great market demand. One of the products that can be obtained indirectly from CO2 is synthetic fuel, produced by the process known as Gas-to- Liquids, or GTL. In this work the technical, economical and potential feasibility of CO2 capture is analyzed, as well as the production of synthetic fuel using the GTL process, offshore, from carbon dioxide (CO2) and methane (CH4), found in the waste chain of the gas treatment in an oil and gas production platform, through dry and steam reforming, followed by Fischer-Tropsch synthesis. Thus, based on literature data and on the use of a commercial process simulator, the simulation of the suggested process was developed and different alternatives to the reutilization of the waste chains were analyzed, including the recycling and burning of some effluent streams. Techniques of energetic integration, optimization and economic analysis of process have also been applied. The results indicated that the process, mass and energy integrated in the condition of lower CO2 emissions and greater financial return, produced synthetic oil in a technically and economically feasible way. The results also indicated that the GTL process, with the technologies used, is not suitable as a method for CO2 capture due to the fact that the generation of this component for the production of synthetic oil is two times greater than the amount fed.

A descoberta de uma nova província petrolífera, conhecida como pré-sal, localizada no litoral brasileiro, representa um novo marco na produção de petróleo mundial. Dentre os vários desafios encontrados para exploração e produção dessa região, a presença de CO2 em grandes concentrações nos fluidos de alguns desses reservatórios tem sido um dos desafios de maior relevância para as empresas que exploram e produzem nessa área (FORMIGLI, 2007). Uma forma alternativa de sequestro do CO2 retirado do gás natural é a sua utilização como matéria prima ou co-alimentação para a síntese de produtos químicos, em especial aqueles com grande demanda de mercado. Um dos produtos que podem ser obtidos indiretamente a partir do CO2 é o petróleo sintético, produzido pelo processo conhecido como Gas-to-Liquids, ou GTL. Neste trabalho foi analisada a viabilidade técnica, econômica e potencial de captura de CO2, da produção de petróleo sintético, pelo processo GTL, offshore, a partir de dióxido de carbono (CO2) e metano (CH4), presentes na corrente de rejeito do tratamento do gás processado em uma plataforma de produção de petróleo e gás, através das reformas seca e a vapor, seguida da síntese Fischer-Tropsch. A partir de dados de literatura e com uso de simulador comercial de processos, a simulação do processo foi desenvolvida e diferentes alternativas para reaproveitamento das correntes residuais do processo foram analisadas, incluindo o reciclo e a queima dos efluentes combustíveis, assim como foram aplicadas técnicas de integração energética, otimização e análise econômica de processos. Os resultados indicaram que o processo, mássica e energeticamente integrado, na condição de menor emissão de CO2 e maior retorno financeiro, produziu petróleo sintético de forma técnica e economicamente viável. Os resultados indicaram ainda que o processo GTL, com as tecnologias utilizadas, não é indicado como método de captura de CO2 devido o fato de a geração desse componente para a produção de petróleo sintético ser duas vezes maior que a quantidade alimentada. / The discovery of a new oil province known as pre-salt, located in the Brazilian coast, represents a new frontier in the world\'s oil production. Among other challenges involved in the exploration and production in that region, the CO2 concentration at high levels in the fluids of some of those reservoirs has been the most relevant challenge for the companies that explore and produce in that area (FORMIGLI, 2007). An alternative to sequestering the CO2 extracted from natural gas is using it as a supply of raw material or as an input to the synthesis of chemical products, especially those with great market demand. One of the products that can be obtained indirectly from CO2 is synthetic fuel, produced by the process known as Gas-to- Liquids, or GTL. In this work the technical, economical and potential feasibility of CO2 capture is analyzed, as well as the production of synthetic fuel using the GTL process, offshore, from carbon dioxide (CO2) and methane (CH4), found in the waste chain of the gas treatment in an oil and gas production platform, through dry and steam reforming, followed by Fischer-Tropsch synthesis. Thus, based on literature data and on the use of a commercial process simulator, the simulation of the suggested process was developed and different alternatives to the reutilization of the waste chains were analyzed, including the recycling and burning of some effluent streams. Techniques of energetic integration, optimization and economic analysis of process have also been applied. The results indicated that the process, mass and energy integrated in the condition of lower CO2 emissions and greater financial return, produced synthetic oil in a technically and economically feasible way. The results also indicated that the GTL process, with the technologies used, is not suitable as a method for CO2 capture due to the fact that the generation of this component for the production of synthetic oil is two times greater than the amount fed.

School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, South Africa August, 2016 / One gram amounts of a commercial iron based catalyst were loaded into three reactors and reduced with syngas, hydrogen and carbon monoxide respectively. Fischer Tropsch experiments on the three reactors in parallel with the same operating conditions, namely 60 mL(NTP)/min, 1 bar gauge and 250 °C, were then conducted for extended periods and the gaseous products analysed. Initially (for about 150 hours) the three catalysts had quite different carbon monoxide conversions. After this until about 1000 hours the conversions were similar. However the distribution of products for the differently reduced catalyst was significantly different. This suggested that permanent changes had been done to the catalysts by the different reducing conditions. To try to understand what the differences during the reduction process might be, a thermodynamic analysis of the solid phases after reduction was done. Unfortunately because all the thermodynamic data for the possible carbides was not available this analysis was of limited value. However it did suggest that hydrogen reduced catalyst might contain more oxides and the carbon monoxide reduced catalyst might contain more carbides. Some electron microscope and XRD experiments supported these ideas and might account for the different selectivities of the differently reduced catalysts. Runs after about 5000 hours were done at different flowrates (60, 30 and 15 mL(NTP)/min) of syngas and again the big effects were on differences between the selectivities, the big effects being when going to the lowest flowrate. After about 12000 hours regeneration of the catalysts was then done by oxidation and then the same syngas reduction on all the catalysts. Runs were then done at different pressures (1, 10 and 20 bar gauge) and again selectivities were the biggest effects that remained, clearly showing the initial reduction had made permanent changes. In the final section some novel plots were used to try to make more sense of the results. It was shown that for all the catalysts the Olefin to Paraffin ratios were tied to each other under all conditions and that they were mainly a function of the conversions with much higher values at low conversions. / MT2017

PhD, Faculty of Engineering and the Built Environment, University of the Witwatersrand / Fischer-Tropsch is a process that converts synthesis gas (especially H2 and CO) into hydrocarbons by the mean of metal catalysts (such as Fe, Co, Ru, and Ni). Its success depends strongly on the catalyst used for the reaction, the reactor where the reaction is taking place, and some parameters such as the operating temperature, the reactor pressure, and the gas purity, composition (ratio H2:CO) and flow rate. Besides the above parameters, other factors, such as the degree of reduction of the catalyst, also play an important role for a successful FT reaction. Water can deactivate (by re-oxidation) the catalyst and carbon deposit can reduce the catalyst’s activity. It is well known that FT is a complex reaction because of the range of products that it produces as well as the reactions that occur during the process. A good choice or combination of catalysts, reactor and operating conditions can help to control the product spectrum. 2 In this thesis we develop a simple graphical technique to represent the mass, energy balance and thermodynamic constraints that affect both the catalyst and the reactor. This graphic model is shown to be capable of opening up insights into reactor operations and indicating preferred operational regions. The diagrams make it possible to visualize operations and understand the interactions between the catalysts and the reactor. The mass and energy balances also provide information about the best possible region in which the FT reactor system can be designed and operated. A few catalysts (Fe/TiO2, Co/TiO2 and Fe:Co/TiO2) were prepared for the completion of this work. Some of them were tested separately and others were mixed in the same reactor. The results showed that the physical mixture (of Fe/TiO2 and Co/TiO2) and bimetallic catalysts behave differently from one another. The addition of Fe Fe/TiO2 to a constant amount of Co/TiO2 results in an increase of CO hydrogenation activity, WGS activity and CH4 selectivity. However, the position of the two catalysts in the reactor (one followed by another) shows little effect on the rate of hydrogenation of CO and the CO conversion.

Due to the combined heavy dependence on crude oil and the unpredictable nature of the associated markets, an alternative means to produce the required hydrocarbon based products is much desired. The Fischer-Tropsch synthesis provides a route to the production of synthetic crude oil by a catalytic reaction between carbon monoxide and hydrogen (collectively referred to as syngas) at moderate temperatures and pressures. First discovered in the early 1900's, the process results in a multitude of products which can supply a range of transportation fuels and petrochemicals. However, knowledge of the reaction process is still not completely understood due to the complex product distribution which is obtained. In order to gain better control over the process outputs, enhancing the understanding of the mechanistic routes which govern the overall reaction is key. A novel route was developed to monitor the number and length of hydrocarbon species which accumulate and grow on the catalyst surface during the reaction by implementing in situ quantitative FTIR spectroscopy. Initially molar absorption coefficients, required in order to quantify the adsorbed hydrocarbon species, were determined utilising a custom made thermogravimetric infrared cell. The resulting absorption coefficients values were then applied to data which was derived from infrared spectra collected for various catalysts during multiple Fischer-Tropsch reactions. The quantitative analysis of the catalyst surface was then compared with reaction data collected using gas chromatography (GC), in order to investigate if a link exists between the surface species and reaction products. Results showed that while no direct link was detected, the observed surface species could be attributed to oxygenate products of the Fischer-Tropsch reaction which are not produced in a detectable amount by GC. The species were shown to reside on both the metal and support material, with the transportation mechanism to the support also investigated.

Fischer-Tropsch synthesis is a commercial technology that allows converting synthesis gas, a mixture of CO and H2, into fuels and chemicals. This process could be one of the actors in the reduction of oil dependency of the transportation sector. In fact, it has great potential for producing synthetic fuels also from renewable sources, such as biomass, after its thermochemical conversion (gasification) into synthesis gas. Concerning the quality of a diesel fuel produced with this technology, it has a lower local environmental impact than conventional diesel, since it is practically free of sulphur and nitrogen compounds and yields lower exhaust emissions of hydrocarbons, CO and particulates. The present study focuses on the use of cobalt-based catalysts for the production of diesel. In particular, it looks upon correlation between product selectivities when varying the catalyst properties and the effect of process parameters, such as a low H2/CO ratio, typical of a biomass-derived synthesis gas, and the water partial pressure. Different cobalt-based catalysts, with different properties, such as conventional 3-dimensional porous network supports (γ-Al2O3, α-Al2O3, TiO2, SiO2), Co-loading, preparation technique, etc., were investigated in the Fischer–Tropsch reaction at industrially relevant process conditions. For a set of process conditions, a linear relationship seems to exist between the selectivity to methane (and other light products) and higher hydrocarbons (identified by the industrially relevant parameter SC5+, selectivity to hydrocarbons with more than 4 carbon atoms) indicating a common precursor. Ordered mesoporous materials (SBA-15), characterized by a 1-dimensional mesoporous network, were tested as model supports and showed the possibility of occurrence of CO-diffusion limitations at diffusion distances much shorter than those required for conventional 3-dimensional porous network supports. The linear relationship mentioned above, derived for conventional supports, was shown to be an efficient tool for indicating whether measured selectivities are affected by CO-diffusion limitations. Some of the catalysts were exposed to H2-poor syngas and to external water addition and the effects on the selectivity relationships were investigated. Furthermore, the possibility of internal water-gas shift of a H2-poor syngas with mixtures of Co/γ-Al2O3 and a Cu/ZnO/Al2O3 catalyst was investigated both as a technical solution for direct use of a model bio-syngas in the Fischer-Tropsch synthesis, and as a means to study the effect of indigenous water removal on the reaction rate to hydrocarbons. It was found that removal of indigenously produced water slows down the reaction rate significantly. Lastly, the effect of water partial pressure on the Fischer–Tropsch rate of the Co catalyst supported on narrow-pore γ-Al2O3, on its own, was studied. Inlet water partial pressure was varied by external water vapor addition at different H2/CO molar ratios ranging from 1 to 3. The effect of water showed to be positive on the rate for all the H2/CO ratios, but more significantly at H2-poor conditions. The nature of this positive effect on the rate seems to be unrelated to changes in amounts of amorphous polymeric carbon detectable by temperature-programmed hydrogenation of the spent catalyst. / <p>QC 20120914</p>

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.

A thesis submitted to the Faculty of Science, University of the Witwatersrand; Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. July 1991 / Precipitated-iron Fischer- Tropsch catalysts were sulfided in the range 500 - 20000 ppm S/Fe with an aqueous sulfide source (Na2S, (NB4)zS, (NB4)zS5) during the precipitation process. Sulfidation was performed at pH 10.75, 8.5 and 6.9. Sodium ions were removed by centrifugation, and atomic absorption analysis confirmed low sodium levels (0-51 ppm). Based on solution speciation models, ferrous sulfide (FeS) which formed from aqueous HS' species, was found to influence the iron-oxyhydroxide crystallite morphology. It is proposed that, when sulfide was added at pH 10.75, FeS molecules functioned as nuclei for crystallite growth, while a pH 6.9 they assisted 'with the aggregation of particles. The processes of nucleation and aggregation appeared to be in competition following sulfidation at pH 8.5, resulting in a composite morphology that produced an inactive catalyst. The bulk structure of the catalysts was elucidated using XRD, SEM and nitrogen porosimetry, All sulfided catalysts exhibited enhanced BET surface areas and total pore volumes with a maximum at 2000 ppm S (surface area = 166 m2/g,total pore volume = 0.254 cm3/g) compared to an unsulfided catalyst (surface area = 58 m2/g, total pore volume = 0.184 cm3/g), Furthermore, for any series of catalysts at the same level of sulfidation, the BET surface areas were observed to decrease as the pH of sulfide addition decreased. Increasing levels of sulfidation (to 20000 ppm) brought about an increase in crystallite size and therefore, improved crystallinity as determined by XRD measurements. Materials with larger crystallites possess smaller surface areas, and thus the crystallinity was found to increase as the pH of sulfidation decreased. Surface characterisation by XPS after calcination at 400°C and reduction (400°C), revealed sulfate species (169.4 eV) on catalysts sulfided with 500-2000 ppm, while sulfide species (162.O eV) emerged at higher sulfide content. No sulfates were observed on reduced catalysts following calcination at 200 C. [Abbreviated Abstract. Open document to view full version]

MSc (Chemistry), Faculty of Science, University of the Witwatersrand, 2002