Fischer-Tropsch Synthesis (FTS) is known as the most practical way to convert natural gas to hydrocarbon products including synthetic fuel depending on the catalysts and operating conditions. Australia has 25% of world's natural gas resources hence Australia's crude oil dependency can be reduced extensively by developing catalysts that will facilitate the technique of converting natural gas to synthetic fuel. Molybdenum nitride has been employed in this study for FTS because of its superior mechanical strength, stability, exceptional resistance to carbon deposition & suifur poisoning. In particular, molybdenum nitride is endowed with similar electronic properties to those of noble metals. Other transition metal nitrides such as Co nitride and Co-Mo nitride were also investigated in this study. The physicochemical attributes of nitride catalysts were examined by BET surface area, particle dispersion, acid site strength & concentration, and surface elemental composition. Gas to solid nitridation kinetic was thermogravimetrically monitored. CO hydrogenation activity was measured in a fixed bed reactor using various syngas compositions and temperatures at atmospheric pressure. The effect of nitridation conditions on catalytic properties of nitrides was investigated via 23 factorial design. It has revealed that nitridation parameters; temperature, nitriding gas composition (H2:NH3) and nitridation reaction time were all significantly influencing catalyst properties. The optimal nitridation condition was 973 K, H2:NH3=1: 1, and 4 hours of nitriding time which gave higher alkene selectivity. 20 wt% M02N/Ah03 was found to be the better FT catalyst compare to catalysts with lower Mo loading and other inorganic oxide supports. Nitridation kinetic studied by thermogravimetric analysis showed that successful nitridation of transition metal oxide precursor was dependent of nitridation temperature and hydrogen concentration. Co-Mo nitride has several forms of nitride species, COS.47N, C03M03N, MoN, and Mo2N. It was shown that COS.47N was the most active component favouring the CO hydrogenation rate and alkene selectivity. Mechanistically-based kinetic models suggested that methanation over Co nitride occurs mainly via surface carbon while surface oxygenated intermediates were accountable for methanation over Co-Mo nitride and Mo nitride.

Thesis (MSc)--University of Stellenbosch, 2005. / Bibliography. Also available via the Internet.

This dissertation research resulted in the development of a Fe based catalyst with Co as a co catalyst, and Ru and ZnO as promoters. The role of Cu and K as promoters and the effect of SiO2 as an alternate support to gamma- Al2O3 were also investigated. A series of Fe-based catalysts for Fischer-Tropsch (F-T) synthesis were prepared. The different promoters were incorporated into the catalyst by impregnation The catalysts were characterized by several methods. The catalytic performance of these materials for F-T synthesis were investigated in a newly designed fixed bed reactor system in the gas phase. It should be noted that the three phase slurry bubble reactors systems are commercially preferred. The reaction conditions were varied for benchmarking the Fe-Zn-K/ gamma- Al2O3 catalyst and for the bimetallic Fe-Co-Zn/ gamma- Al2O3 catalyst and to identify optimal process parameters for further catalyst designs. The H2:CO ratio used in this study was 2. The newly designed catalysts showed significantly high activity towards CO conversion (>70 %), along with low selectivity towards CO2 (5 -15 %) and methane (ND - 3 %). The data show that varying the process conditions, it is possible to achieve narrow distribution of the liquid products. The results employing Fe-Zn-K catalysts showed that an increase in pressure increased the mean carbon chain length. In contrast, an increase in temperature resulted in a decline in the average carbon chain length. Increasing the feed flow rate, or in other words decreasing the residence time of the reactants and the intermediates, resulted in a decrease in the average carbon number in the product hydrocarbons. The evaluation of the effect of process conditions on the performance of Fe-Co-Zn catalysts revealed that the effect of pressure on the carbon chain length was reversed. Increasing the pressure from 250 to 350 psig decreased the carbon chain length. The increase in temperature, however, resulted in a decrease in the carbon chain length as observed in the Fe-Zn-K catalysts. Fe catalysts groups containing different proportions of Co were prepared. It was determined that an Fe:Co ratio of 4:1 is sufficient to obtain high CO conversions with a high selectivity towards liquid hydrocarbons. The hydrocarbon distribution on the other hand remained almost unchanged due to a change in the Co content. The use of silica, as opposed to alumina as the catalyst support, enhanced the CO conversion and the selectivity of the process towards liquid hydrocarbons. The methane and CO2 selectivities on both the supports remained unchanged. However, a significant difference in the liquid hydrocarbon distribution was observed. Addition of K to the catalyst resulted in a change in the liquid hydrocarbon distribution in that a slight increase in the heavier hydrocarbons was observed. A series of Fe4Co1Zn0.04 based catalysts for Fischer-Tropsch (F-T) synthesis, in which the different amounts of Ru are incorporated by the impregnation were also studied. The results showed the incorporation of Ru suppressed the CH4 formation at the cost of increasing the CO2 selectivity.

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Curso de Pós-Graduação em Físico-Química / Made available in DSpace on 2012-10-16T01:18:50Z (GMT). No. of bitstreams: 0Bitstream added on 2016-01-08T15:46:06Z : No. of bitstreams: 1 202998.pdf: 4722121 bytes, checksum: 2b154256d729c37d2fe8bf2aae06aee7 (MD5)

The focus of this research was to investigate the role of carbon nanotubes as active catalysts in the Fischer-Tropsch reaction to derive liquid fuels from synthesis gas. Carbon nanotubes (CNTs) have unique structural and mechanical properties that make them ideal catalyst supports, but they also exhibit catalytic potential as well. This study implored the use of multi-walled CNTs on different substrates and single-walled CNTs grown from various precursors to analyze the effectiveness of the CNTs in FT synthesis. Multi-walled nanotubes (MWNTs) were tested on two different substrates: alumina pellets and inconel. The MWNTs on the alumina substrate yielded nearly all alkane and alkene products, with very little aromatic products. The amount of converted syngas reached 97% but had a high liquid product selectivity to methane, at roughly 57%. The MWNTs on inconel substrate produced nearly 80% aromatic products in one stage of the experiment, while the other three stages produces almost all alkane products with little oxygenates. Much of the liquid product yield (upwards of 73%) was between C10 and C21, which is ideal for diesel fuel. Single-walled nanotubes (SWNTs) were also tested in the FTS. All of the SWNTs were tested under a series of 6 temperatures, 300psig, and a syngas ratio of 1:1. Iron, nickel, and cobalt, which have all been proven as effective FT catalysts, were tested in trace amounts with CNTs. Fe-SWNTs (ferrocene assisted SWNTs) yielded a product of 100% C7 and C8 carbon species at two of the temperatures while 3 of the temperatures held a combination of longer chained alkanes, of C18 and longer. However, the last temperature converted 100% of the feedgas into methane and CO2. The product selectivity to CH4 and CO2 posed a problem with the Fe-SWNTs catalyst, where in all temperatures the selectivity exceeded 80%. Ni-SWNTs (nickellocene assisted SWNTs) yielded slightly better results with a higher selectivity to C2-C7, but no selectivity to longer chained hydrocarbons. Co-SWNTs (cobaltocene assisted SWNTs) tested under the same parameters yielded similar results as the Fe-SWNTs, with a very high selectivity to CH4 and CO2. Only at temperatures of 300 and 250°C were there any selectivity to compounds other than CH4 and CO2, but less than 10% selectivity to those alkanes (C2+). The final experiment consisted of a catalyst prepared from a feed solution containing a mixture of ferrocene and nickellocene. The Fe+Ni-SWNT catalyst underwent the same conditions as the other SWNT catalysts, this combination yielded favorable results with over 98% conversion of syngas over all temperatures and a high selectivity to shorter chain length hydrocarbons, namely alkanes of chain lengths between C2 and C7. Although the higher temperatures did show a selectivity to methane (roughly 45%), the CO2 selectivity was rather low, below 10% (except at 450°C, which pushed 20%).

ABSTRACT This thesis presents the results from research conducted on Fischer-Tropsch synthesis (FTS) in supercritical CO2 from syngas (H2:CO =1:1) typically produced from coal gasification and using a Fe-Zn-K catalyst. Experiments were conducted with syngas alone at different pressures (200 psi - 1050 psi) and temperatures (275, 350 and 375 oC). Experiments were also conducted with a syngas pressure of 200 psi and at different partial pressures of an inert diluent (N2) such that the total pressure varied from 200 psi to 1050 psi. Finally, experiments were conducted with CO2 as a diluent and at a syngas pressure of 200 psi. The CO2 partial pressure was increased from 0 psi to 1400 psi (non critical to supercritical conditions). The data show an enhancement in the hydrocarbon selectivity and reduction in the parasitic loss of carbon efficiency due to CO2 formation along with significant improvement in the conversion rates. The experiments were conducted in a unique reactor setup that can conduct gas phase or supercritical phase FT synthesis in both batch or flow modes. The use of the supercritical CO2 (ScCO2) inhibited both CH4 and CO2 selectivities while enhancing the rates of synthesis. In addition, the use of supercritical CO2 is expected to prolong the life of the catalyst presumably by removing the heat of reaction from the catalyst's surface and solubilizing the waxes that tend to deposit on the surface. Although not within the scope of this thesis, the products from such a reactor system can be easily separated without the need of an additional unit process simply by tuning the pressure and temperature. The product spectrum and the selectivities for the different products are presented for each set of experiments. The effects of process parameters such as temperature, pressure, N2 partial pressure, and CO2 partial pressure on the product spectrum are also discussed. The clear increase in CO conversion at H2:CO ratio of 1:1 in supercritical phase as compared to gas phase reaction, the decrease in CO2 and CH4 selectivity, and an overall shift in the product distribution towards higher hydrocarbons have been demonstrated. Thus the use of supercritical CO2 has the potential through the FT process to convert coal to liquid fuels using Fe based catalysts, especially since the reactions can be conducted in a two phase regime without losing the benefits of the 3-phase slurry reactor systems

With increasing oil prices and attention towards the reduction of anthropogenic CO2, the use of supercritical carbon dioxide for Fischer Tropsch Synthesis (FTS) is showing promise in fulfilling the demand of clean liquid fuels. The evidence of consumption of carbon dioxide means that it need not to be removed from the syngas feed to the Fischer Tropsch reactor after the gasification process. Over the last five years, research at SIUC have shown that FTS in supercritical CO2 reduces the selectivities for methane, enhances conversion, reduces the net CO2 produces in the coal to liquid fuels process and increase the life of the catalyst. The research has already evaluated the impact of various operating and feed conditions on the FTS for the once through process. We believe that the integration of unreacted feed recycle would enhance conversion, increase the yield and throughput of liquid fuels for the same reactor size. The proposed research aims at evaluating the impact of recycle of the unreacted feed gas along with associated product gases on the performance of supercritical CO2 FTS. The previously identified conditions will be utilized and various recycle ratios will be evaluated in this research once the recycle pump and associated fittings have been integrated to the supercritical CO2 FTS. In this research two different catalysts (Fe-Zn-K, Fe-Co-Zn-K) were analyzed under SC-FTS in different recycle rate at 350oC and 1200 psi. The use of recycle was found to improve conversion from 80% to close to 100% with both catalysts. The experiment recycle rate at 4.32 and 4.91 was clearly surpassing theoretical recycle curve. The steady state reaction rate constant was increased to 0.65 and 0.8 min-1 for recycle rate of 4.32 and 4.91 respectively. Carbon dioxide selectivity was decreased for both catalyst as it was converting to carbon monoxide. Carbon dioxide consumption was increased from 0.014 to 0.034 mole fraction. This concluded that CO2 is being used in the system and converting which created the concentration of the feed gas higher inside the reactor. The research has provided the best conditions for the enhanced conversion while minimizing CO2 formation. Though this research was not able to provide the optimal recycle rate it have created the path for the future research to proceed in the right direction. This reduction and utilization of CO2 will help to reduce the cost of carbon dioxide removal and saves the environment from carbon dioxide emission.

BARROS JÚNIOR, A. F. Modelagem e simulação da síntese de Fischer-Tropsch em reator tubular de leito fixo com catalisador de ferro. 108 f. 2008. Dissertação (Mestrado em Engenharia Química) – Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2008. / Submitted by Marlene Sousa (mmarlene@ufc.br) on 2016-03-22T14:53:12Z No. of bitstreams: 1 2008_dis_afbarrosjunior.pdf: 2062057 bytes, checksum: 235fcbada7e9fcecaab18486e3bf59a8 (MD5) / Approved for entry into archive by Marlene Sousa(mmarlene@ufc.br) on 2016-03-28T18:01:01Z (GMT) No. of bitstreams: 1 2008_dis_afbarrosjunior.pdf: 2062057 bytes, checksum: 235fcbada7e9fcecaab18486e3bf59a8 (MD5) / Made available in DSpace on 2016-03-28T18:01:01Z (GMT). No. of bitstreams: 1 2008_dis_afbarrosjunior.pdf: 2062057 bytes, checksum: 235fcbada7e9fcecaab18486e3bf59a8 (MD5) Previous issue date: 2008-10-20 / In this work, a fixed-bed tubular reactor was modeled and simulated for the Fischer-Tropsch synthesis carried out using iron-based catalysts. The model has considered the fluid-dynamics of the fixed-bed reactor and the polymerization reaction of the Fischer-Trospch synthesis. Several simulations were carried out with the mathematical model to study the effects of the operating conditions on the product distribution and on the yield into hydrocarbons. The simulations were analyzed aiming the optimization of the system toward the production of diesel and wax fractions, which can be later cracked to produce a higher amount of liquid products. The simulations were carried out following a factorial design to identify the operating conditions that most influence the production of each specific product fraction, as gasoline, diesel and waxes, and in the yield of synthesis gas into hydrocarbon / A necessidade de produção de combustíveis líquidos, principalmente diesel com baixos teores de enxofre para atender recentes legislações ambientais, impulsionou a pesquisa sobre a reação de síntese de Fischer-Tropsch (SFT), que utiliza a polimerização entre monóxido de carbono (CO) e hidrogênio (H2) em diversos tipos de reator e de catalisador. Foram realizadas várias simulações da reação de síntese de Fischer-Tropsch em reator tubular de leito fixo com catalisador de ferro avaliando-se o efeito de determinadas condições operacionais na distribuição de produtos, de acordo com o modelo desenvolvido para a distribuição das massas moleculares dos hidrocarbonetos formados. As condições operacionais foram avaliadas de modo favorecer a formação de diesel e graxa, que por sua vez podem ser craqueadas visando à produção de combustíveis líquidos. Um planejamento experimental e uma posterior análise estatística foram executados de forma a apontar as condições operacionais que mais influenciam na formação de produtos específicos como gasolina, diesel e graxas, assim como na conversão do gás de síntese em hidrocarbonetos. Os resultados obtidos mostraram a adequação da modelagem adotada com dados experimentais existentes na literatura

Iron carbides are amongst the crystalline phases formed during Fischer-Tropsch synthesis to produce hydrocarbons (Dry, 1990, Niemantsverdriet et al., 1980), using iron catalysts. The small crystallite size of the iron carbides causes peak broadening in XRD and prevented complete structure determinations in the past (Hagg, 1931; Retief, 1999; Senateur et al., 1962). Fortunately new instrumentation and techniques, such as fast powder X-ray diffractometers and software for structure determination, are now available to study crystal structures. Five different iron carbide phases are known to form during Fischer-Tropsch synthesis i.e. Hägg carbide (χ-Fe5C2), pseudo-hexagonal iron carbide (έ- Fe2.2C), hexagonal iron carbide (ε-Fe3C), Eckström-Adcock iron carbide (Fe7C3) and cementite (θ-Fe3C). Since the structure of cementite θ-Fe3C is well-known (Westgren & Phragmen, 1922) this study focused on the remainder, i.e. the determination of the crystal structures of the first four iron carbides: Hägg carbide (χ-Fe5C2), pseudo-hexagonal iron carbide (έ -Fe2.2C), hexagonal iron carbide (ε-Fe3C) and Eckström-Adcock iron carbide (Fe7C3). This study consisted of the preparation of iron carbides, structure determinations of these iron carbides, determination of reactions of the iron carbides during Fischer-Tropsch synthesis (FTS) (in situ XRD) and the stability of Hägg carbide (χ-Fe5C2) during FTS under commercial fixed bed reactor conditions. Time-temperature-transformation graphs were determined for iron catalysts with and without potassium promoter. The first step in the structure determination process was the preparation of almost pure samples. Samples of Hagg carbide (:t-FesC2), pseudo-hexagonal 8 -Fe22C iron carbide and hexagonal 1::-Fe3C iron carbide were prepared as pure as possible using the Anton Paar XRK600 reaction chamber attached to an X'Pert Pro multi-purpose diffractometer (N!PD). Eckstrom-Adcock iron carbide (Fe7C3) was available in spent catalyst from a fluidized-bed hydrocarbon synthesis plant at SASOL. These samples were characterized using room temperature and low temperature (77 K) Moss bauer absorption spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM, Philips CM200). Thermo-gravimetric analysis and conductivity measurements were done to characterize the carbonaceous species in the samples. Molecular modelling calculations were done using CASTEP (N!ilman et al., 2000; Payne et al., 1992) to determine the total lattice energies of the iron carbide structures.... / Prof. G.J. Kruger Prof. J.P.R. de Villiers

The global community has accepted Fischer Tropsch synthesis as one of the sustainable pathways to transportation fuels and chemicals due to the ever-depleting reserves of fossil fuels and its detrimental impact on the environment. However, the high capital investment and operating expenses associated with this technology have hampered its ability to compete with conventional petrochemicals. Some of the operating costs emanate from the choice of catalyst precursors and operational problems, which could lead to plant shutdowns. In recent times, few efforts have been made to explore cheaper FT catalysts to reduce operational costs, but the mechanical strength of solid FT catalysts, especially for pilot-scale fixed bed operations is not well represented in open literature. As a result, there is a high prevalence of mechanical failure of solid FT catalysts in pilot fixed-bed applications. In this study, we propose a scalable, Fischer Tropsch iron ore catalyst that is mechanically suited for fixed bed reactors to help address this issue. The catalyst development of the proposed iron ore catalyst involved the slurry phase impregnation of the precursor with copper and potassium and then shaping into spherical pellets with mass additions of 10%, 15% and 20% of bentonite(binder) on a rotating drum. There afterwards, the mechanical strength of each pelletized catalyst was tested using the single pellet crushing testing method (ASTM D 4179). These results were compared to the crushing strength of commercial spherical alumina to ascertain their suitability for fixed bed reactors. The most robust solid catalyst was the 10% binder iron ore pellets which recorded a single pellet crushing strength of 1833 kPa and was more than three times that of commercial spherical alumina and thus deemed apt for fixed bed reactors. A unique statistical approach was used to study the mechanical strength of the various binder combinations due to scattering in single pellet crushing strength data. The analysis revealed that the 10% binder iron ore pellets were most suited for laboratory FT runs and thus was tested for its catalytic performance. The FT runs revealed that the 10% binder iron ore catalyst had a CO conversion of 72.1 % and comparable to other similar iron-based FT catalysts reported in the literature. The proposed catalyst also showed a CH5+ selectivity of 83.2%, which was comparable the ones reported by other researchers. These findings provide a simple and cost- effect approach to upscale laboratory-scale FT catalyst designs to pre-emp its performance in pilot or industrial scenarios. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)