Rozprawy doktorskie: „Fischer Tropsch Catalysts”

1

Harle, Gavin John. "Polyoxometalate models for Fischer-Tropsch Catalysts". Thesis, University of Newcastle Upon Tyne, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.519568.

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Gallagher, James R. "Accelerated discovery of Fischer-Tropsch catalysts". Thesis, University of Liverpool, 2013. http://livrepository.liverpool.ac.uk/10793/.

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Progress in catalyst development for reactions such as Fischer-Tropsch synthesis (FTS) has been impeded by the time consuming characterisation and catalytic testing of new formulations. Hence, this thesis discusses the development of high-throughput (HT) techniques for studying the deactivation of cobalt based catalysts under simulated FTS conditions. Libraries were rapidly synthesised by incipient wetness methods utilising robotic platforms and then treated in arrays under conditions designed to cause rapid ageing. HT X-ray diffraction (XRD) was performed before and after the ageing test to monitor the deactivation of the catalysts by sintering of the active metal particles or loss of metallic cobalt. HT thermogravimetric analysis in 5 % H2 was utilised to probe the reducibility of the catalysts and this information was then combined with results from XRD to inform decisions on which formulations to scale-up for further testing. This approach led to the discovery of highly stable Co/Ru/Mg/γ-Al2O3 catalysts. Thorough characterisation of selected hits was carried out to understand the phase assemblage. In addition to the high stability of Co/Ru/Mg/γ-Al2O3 catalysts, there was also a lowering of intrinsic activity. The degree to which the intrinsic activity was decreased was dependent on the amount of Mg in the catalyst and more specifically, the amount of Mg in close proximity to Co as identified by the amount of Mg incorporated into MgxCo3-xO4 phases prior to activation. In addition to incipient wetness synthesis, a method was also developed to perform HT co-precipitation synthesis with the aid of robotic platforms. HT synthesis was coupled with HT XRD to determine synthesis conditions giving rise to high surface area, phase-pure magnesium aluminate supports.

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Zwane, Seneliso T. "Vanadia Promoted Co-AI20 3 Fischer-Tropsch Catalysts". Master's thesis, University of Cape Town, 2004. http://hdl.handle.net/11427/6760.

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Bibliography: leaves 117-124.
The primary aim of this work was to study systematically V20 5 promotion on yAI203 supported cobalt-based Fischer-Tropsch catalysts. The y-Ah03 support was modified by addition of varying amounts of vanadia and was subsequently loaded with the same Co content (10 wt-%). The modified supports and catalysts were characterised using conventional characterisation methods. The physio-chemical properties of the vanadia promoted supports and catalysts were characterised using Atomic Adsorption Spectroscopy (AAS), zeta-potential measurements, and BET measurements, X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR), Transmission Electron Microscopy (TEM), and CO chemisorption. Catalyst performance in the Fischer-Tropsch synthesis was tested in fixed bed reactor. A catalysts synthesised from plain y-A1203 was used as a base catalyst. Characterization results show that modification of y-Ab03 support to obtain V205 loadings beyond 1-monolayer vanadia coverage was difficult when using ion exchange. Ion-exchange equilibrium limitations might have caused the poor vanadia loadings beyond 1-monolayer coverage. The supports net surface charge as measured using zeta potential, was decreased by vanadia content in the supports. CO chemisorption results were complex and could only be modelled using dual site Langmuir model assuming the presence of two different sites absorbing CO on the Co-V-AI catalyst system. This made extraction of physical properties from this method rather difficult. Fischer Tropsch synthesis reaction was carried out at typical industrial conditions (T=220°C, P=20 bar (a), H2/CO=2 Xco-60 mol-%) for cobalt catalysts. Vanadia promoted catalysts showed a marked decrease in initial activity. However, the overall deactivation rate was lower with increasing vanadia content. The vanadia content did not affect the chain growth kinetic behavior of the catalyst in the Fischer-Tropsch synthesis hence C5+ selectivity in the Fischer-Tropsch synthesis was unperturbed by vanadia content. Increasing the vanadia content in the catalyst resulted in high n-olefin content and high 1-olefin content. The observed increase in olefin content might be due to the low catalytic activity observed for the catalysts with high vanadia loadings. The most pronounced effect of vanadia promotion on Fischer Tropsch synthesis was in the oxygenate content in the Fischer-Tropsch product. Catalysts with high vanadia loading yielded high amounts of oxygenate products; mainly alcohols and aldehydes.

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Long, Helen Clare. "A mechanistic study of the Fischer-Tropsch reaction". Thesis, University of Sheffield, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.387655.

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Kraum, Martin. "Fischer-Tropsch synthesis on supported cobalt based Catalysts Influence of various preparation methods and supports on catalyst activity and chain growth probability /". [S.l. : s.n.], 1999. http://deposit.ddb.de/cgi-bin/dokserv?idn=959085181.

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Mogorosi, Ramoshibidu Patrick. "Metal-support interactions on Fe-based Fischer-Tropsch catalysts". Doctoral thesis, University of Cape Town, 2012. http://hdl.handle.net/11427/5438.

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Includes abstract.
Includes bibliographical references.
‘Metal support interactions’ is a term used to describe a phenomenon whereby the interaction between the active metal and the support material is strong enough to affect the catalytic activity and selectivity of the active phase. Primarily, there are two theories described in literature to explain the manner in which the development of these interactions alters catalytic behavior in supported catalysts. The first theory is ‘the contact affect’, which is generally associated with partially reducible supports such as TiO2 [Tauster et al., 1978]. It is believed that the intimate contact between the partially reduced surface of the support and the surface of the active phase results in the creation of special contact sites at the interface. These sites are thought to be responsible for the improved activity observed in TiO2 supported catalysts [Burch and Flambard, 1982; Vannice and Sudhakar, 1984; Tauster, 1987]. The second theory is ‘the ligand effect’. With this hypothesis, it is proposed that the development of chemical bonds at the interface between the active metal and the support material is responsible for the altered catalytic behavior in supported catalysts [Qing et al., 2011; Sou et al., 2012]. The presence of these bonds is believed to alter the strength of CO and H2 absorption on the surface of the active phase, resulting in different activity and selectivity. These chemical bonds might be viewed as ligand attachments [Haller and Resasco, 1989], holding the active metal in place. The ligand effect is commonly associated with irreducible support material such as silica [Hou et al., 2008; Sou et al., 2012] and alumina [Taniguchi, et al., 1988; Wan et al., 2007]. The aim of this study was to investigate metal support interactions as a ligand effect. The objective was to prepare model catalysts and modify the surface of the iron oxide using alkoxide compounds, viz. tetra ethoxy-silane (TEOS) and titanium butoxide (TBO), to generate the Fe-O-Si and Fe-O-Ti interactions respectively in a controlled and varying manner in order to investigate how these interactions affect the behaviour of the catalysts. The presence of both the surface silicate and surface titanate groups in the calcined catalyst precursor was confirmed using DRIFTS. Characterization of the calcined samples, containing Fe2O3, showed an overall decrease in the average crystallite size with increasing alkoxide loading (for both TEOS and TBO). However, this effect was more severe for the TEOS modified samples.

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Petersen, Anna Paula. "Alumina-modified cobalt catalysts for the Fischer-Tropsch synthesis". Doctoral thesis, University of Cape Town, 2018. http://hdl.handle.net/11427/29395.

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In the Fischer-Tropsch process, valuable hydrocarbons are produced using the basic starting materials hydrogen and carbon monoxide, which can be derived from alternative carbon sources such as coal, gas or biomass [1]. Although this process has been studied for almost a century, the effects of the support material on activity, selectivity and stability of the catalyst remain obscure. This study aims to gain fundamental insights into the effect of metal-support interactions in cobalt alumina based Fischer-Tropsch catalysts. To accomplish this, the effects of metal-support interactions have to be isolated from possible convoluting effects of the metal crystallite size and support porosity. This is achieved by preparing inverse-model catalysts, in which the support is deposited onto the metal, in contrast to conventional supported catalysts, in which the metal phase is deposited onto a porous support [2]. Cobalt alumina inverse-model catalysts were prepared by incipient wetness impregnation of cobalt oxide with aluminium sec-butoxide. The alumina loading was varied systematically between 0 and 2.5 wt% Al. The catalysts were characterised by X-ray diffraction (XRD), Transmission electron microscopy (TEM), H2 -chemisorption, and X-ray absorption near edge spectroscopy (XANES). The catalyst reducibility was studied by temperature programmed reduction (TPR), in situ (XRD) and in situ (XANES) experiments. The catalytic performance for the Fischer-Tropsch synthesis was studied in a slurry reactor under industrially relevant conditions. The alumina modification was found to prevent sintering and decrease the reducibility of the catalysts. With increasing alumina loading, and increasing calcination temperature, reduction peaks shifted to higher temperatures and peaks with maxima above 400 ˝C appeared in the TPR. The kinetic evaluation showed that the decreased reducibility was due to a decrease in the pre-exponential factor, which suggests that the alumina modification hindered hydrogen activation and/or nucleation of reduced cobalt phases. The activity of the catalysts for the FT reaction was found to increase with increasing alumina loading. This was likely an effect of the increase in metal dispersion upon alumina modification. Furthermore, alumina-modified catalysts had a higher C5+ and olefin selectivity, and lower methane selectivity. Pyridine-TPD experiments showed that the alumina modification introduced Lewis acid sites to the cobalt catalysts. Lewis acid sites may interact with adsorbed CO thereby weakening the C-O bond and facilitating CO dissociation. This was supported by CO-TPR experiments, which revealed that alumina-modified catalysts had an increased activity for the surface catalysed Boudouard reaction. It is concluded that the alumina modification increased the rate of CO dissociation on metallic cobalt. An increased rate of CO dissociation may lead to coverage of the metal surface with carbon thereby decreasing hydrogenation and shifting the product selectivity towards high molecular weight products. Hence, alumina may promote the selectivity of cobalt catalysts via a synergistic effect.

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Paul, Uchenna Prince. "Microkinetic Model of Fischer-Tropsch Synthesis on Iron Catalysts". Diss., CLICK HERE for online access, 2008. http://contentdm.lib.byu.edu/ETD/image/etd2535.pdf.

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Cook, Kari Marie. "Understanding Noble Metal Addition in Cobalt Fischer Tropsch Catalysts". BYU ScholarsArchive, 2012. https://scholarsarchive.byu.edu/etd/3293.

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The effects of noble metal (NM) promotion and deposition order (co-deposition of NM with the final Co deposition [co-dep] or sequential deposition of NM after Co deposition [seq-dep]) on surface area, pore size, metal retention, crystallite size, noble metal distribution and bonding in Co Fischer Tropsch (FT) catalysts were studied as were the resulting Co reducibility and Fischer Tropsch activity/selectivity properties. Catalysts containing nominally 25wt% Co with either 0.3 wt% Ru, 0.58 wt% Pt, 0.55wt% Re, or no NM on a La-stabilized-Al2O3 support were prepared by wet deposition. The Co, Pt, and Re were uniformly dispersed, but Ru distribution and retention were problematic and deposition-order dependent—85% was lost with co-dep, but it was uniformly distributed while 54% was lost with seq-dep and it was concentrated at the pellet edge. The co-dep catalysts all have smaller reduced Co crystallite size than their corresponding seq-dep catalysts. The average crystallite diameters for all 3 co-dep catalysts are between 4.1 and 4.3nm and ~90% of the crystallites are < 6nm. XAFS measurements showed that after reduction at 360°C, Pt is bonded with Co even with mild calcination between the final Co and the Pt deposition. On the other hand, neither Ru nor Re formed direct bonds with Co. Ru remained in a separate metal phase after reduction even at low loadings. Re remained as Re2O7 and still promoted Co reduction well (e.g. 42% reduced to Co metal compared to none for the unpromoted catalyst). By all measures of reducibility (TPR, EOR, H2 uptake), all NM promoted catalysts were more reducible than the unpromoted catalyst. The co-dep catalysts have lower TPR peak temperatures, but lower extents of reduction than their corresponding seq-dep catalysts. The NM type effect on overall extent of reduction trend was Co/Pt-seq>Co/Re-seq>Co/Ru-seq=Co/Pt-co>Co/Re-co>Co/Ru-co>Co. The Co/Pt-co catalyst was the most active of all the catalysts both on rate per mass and per site basis. The co-dep catalysts were all more active than the corresponding sequentially deposited catalysts. The co-dep Pt and Re catalyst activity is greater due to higher activity per site, while co-dep Ru activity is greater due to a higher abundance of active sites.

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Miller, Steven. "Characterization of Potassium Promoted & Unpromoted Fischer-Tropsch Catalysts". TopSCHOLAR®, 1985. https://digitalcommons.wku.edu/theses/2628.

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The technique of x-ray photoelectron spectroscopy (XPS) has been applied to characterize iron-manganese catalysts used in Fischer-Tropsch synthesis. The catalysts, which vary in composition from 10 FE/90 Mn, to 50 Fe/50 Mn are analyzed after being placed in a slurry reactor and having synthesis gas reacted over them. Changes, in catalyst composition are investigated further using in situ techniques. Additionally, 20 Fe/80 Mn catalysts containing potassium in the range of 0.1 wt.% to 1.3 wt.% are analyzed in the same manner. These studies have permitted the identification of some of the factors influencing activation and deactivation, product selectivity, and surface speciation.

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Lualdi, Matteo. "Fischer-Tropsch Synthesis over Cobalt-based Catalysts for BTL applications". Doctoral thesis, KTH, Kemisk teknologi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-102304.

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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.

QC 20120914

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McNab, Andrew Irvine. "Quantification and qualification of species adsorbed on Fischer-Tropsch catalysts". Thesis, University of Aberdeen, 2017. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?pid=235995.

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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.

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Patterson, Veronica A. "The effects of carbon deposition on catalyst deactivation in high temperature Fischer-Tropsch catalysts". Thesis, University of St Andrews, 2012. http://hdl.handle.net/10023/3086.

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In this work, carbonaceous deposits on spent HTFT catalysts were investigated. This research was required in order to better understand the observed loss in productivity observed in the industrial reactors, with the aim of improving the economy of the HTFT process. A host of complementary techniques were employed to systematically determine the composition of a typical catalyst recovered from a reactor. Spent HTFT catalysts are comprised of magnetite and a mixture of iron carbides as well as adsorbed hydrocarbon products (soft carbon) and hard carbon. Reaction initiates at the particle surface and along the promoter-rich grain boundaries toward the core of the grains. A partially reacted particle would therefore have a core-shell structure, with magnetite representing the unreacted region of the catalyst. The reacted region consists of a porous carbonaceous matrix with soft carbon and carbide crystallites nestled in this matrix. The hard carbonaceous species is a mixture of polymeric carbon and polycyclic aromatic hydrocarbons. The particle structure is linked to the sample preparation method and an alternative method yielding catalyst particle with uniformly distributed promoter elements could be beneficial. Investigating carbonaceous species is a complex process, and development of a fresh methodology would aid in the quest for insight into the nature of carbonaceous species in various systems. A new approach which entails a combination of the traditional techniques combined with MALDI-TOF MS enabled a deeper investigation. Additional aspects such as the molecular weight distributions along with known information about crystallinity and morphology of the catalyst provide a comprehensive study of carbonaceous material. Polymeric carbon and very large polycyclic aromatic hydrocarbons constitute hard carbon and can be observed with minimal sample preparation procedures. The evolution of the HTFT catalysts was investigated as a function of time-on-stream. This enabled us to study the effects of increasing amounts of hard carbon on the activity and the chemical and physical properties of the catalysts. The catalyst activity was found to decrease with increasing hard carbon content, although the effect of carbon deposition cannot be distinguished from phase transformation (oxidation) which occurs simultaneously. A method to quantify the amount of hard carbon, which progressively builds up on the catalyst, was demonstrated. This required a great deal of method development, which provides a platform for future investigations of these catalysts. Importantly, it allows predictions of the amounts of carbon that will be deposited after a certain reaction time. This allows more efficient regulation of catalyst replacement. The production of fine carbon-rich particles in the industrial reactor poses a major problem in the process. Carbon deposition leads to an increase in particle diameter with time on-stream. Permissible levels of hard carbon were identified, beyond which the mechanical strength of the catalyst particles deteriorate. This leads to break-up of the particles and therefore fines formation. The surface area and pore volume generally increase with progressive deposition of hard carbon, while the bulk density of the catalyst material exhibits a linear decrease with carbon build-up. A mechanism is proposed for hard carbon formation which apparently occurs through the dissociative adsorption of CO to form a carbon monolayer. This is followed by polymerisation of the carbon atoms. Meta-stable interstitial carbides are formed at the iron-carbon interface. Owing to a carbon concentration gradient between the top of the surface and the bottom of the metal or carbide particle, carbon diffusion across the crystal (carbide decomposition) and grows as a PAH molecule lifting the iron carbide away from the particle. As this corrosion process is intrinsic to iron-based catalysts, a catalyst that contains sulphur is proposed for future development.

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Elorriaga, de la Fuente Ibone. "Noble Metal Catalysts for the Hydrocracking of Fischer-Tropsch waxes". Thesis, KTH, Skolan för kemivetenskap (CHE), 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-156376.

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Fischer-Tropsch synthesis enables the production of high quality diesel fuel from biomass derived synthesis gas. In order to increase the overall diesel yield, it is necessary to perform a subsequent hydrocracking of the long-chain linear paraffins. This work is focused on characterization and testing of catalysts for the hydrocracking reaction of Fischer-Tropsch waxes. In particular, noble metal catalyst based on Pt and Pd on amorphous silica-alumina support were tested. Palladium based catalysts performed nearly an ideal bifunctional mechanism, while platinum based catalysts performed another way of cracking: hydrogenolysis. Platinum based catalysts are more active than palladium ones, with the same metal loading. This is a consequence of the nature of the metal sites. The product distribution is similar for both platinum and palladium catalysts. However, due to the hydrogenolysis cracking mechanism performed by platinum based catalysts, the amount of light gases produced on platinum based catalysts is higher. Furthermore, the deactivation behavior of the Platinum and Palladium catalysts has been studied, and the results showed that the dispersion of the active phase decreased with deactivation and the average crystallite diameter increased. This means a decrease in activity. A regeneration program, temperature programmed oxidation (TPO), has been carried out demonstrating that the activity was not completely recovered.

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Huh, Billy K. "Structural effects in Fischer-Tropsch synthesis over bimetallic supported catalysts". Diss., Georgia Institute of Technology, 1985. http://hdl.handle.net/1853/11832.

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Zhuang, Youqi. "The performance of structured cobalt catalysts in Fischer-Tropsch synthesis". Doctoral thesis, University of Cape Town, 2009. http://hdl.handle.net/11427/5381.

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Cobalt is the preferred catalyst metal for the production of clean burning, high cetane number diesel fuel from synthesis gas using the Fischer-Tropsch synthesis. Hence, increasing C5+ selectivity of cobalt catalysts is one of the hot topics in Fischer-Tropsch synthesis. Internal mass transport limitation may affect C5+ selectivity. It was concluded that mild transport limitation is required for maximum C5+ selectivity. Mild transport limitation also increases the catalyst activity, since the reported Fischer- Tropsch rate of reaction has a negative dependency on CO partial pressure. The metal distribution within catalyst pellets may modify product selectivity by changing the local metal density and the diffusion path length. However, current catalyst preparation methods limit metal distribution in transition metal catalysts. The aim of this study is to explore a possible catalyst synthesis route for egg-shell, egg-yolk and egg-white type of cobalt catalyst pellets. The establishment of the nonuniform cobalt catalyst synthesis method will provide an observational evaluation technique for the investigation of the effect of intra-pellet metal distribution on the activity and product selectivity of the Fischer-Tropsch synthesis. The non-uniform catalyst synthesis method utilises the hydrophobic nature of the silica pellet. Egg-shell, egg-yolk and egg-white type of cobalt catalyst with sharp metal enriched boundary were synthesized. The intra-pellet cobalt distribution, metal particle size, metal loading, metal surface area and catalyst reducibility were characterised. The performance of these non-uniform catalysts was tested in a modified slurry type reactor. Catalyst pellets were kept in mesh-wire baskets which were mounted inside a slurry reactor, and tested in the absence of external mass transport limitation. The Fischer-Tropsch activity was recorded and modelled using a reaction-diffusion pellet inside a continuous stirred tank reactor model. The product selectivity were analysed with an offline GC. The Fischer-Tropsch activity is strongly dependent on the intra-pellet metal distribution. The egg-shell type of catalyst outperforms the uniform, egg-yolk and eggwhite type of catalyst, in terms of activity, under the influence of internal mass transport limitation. The intra-pellet distribution alters the reactant concentration in the pellet as well as intra-pellet H2/CO ratio. The reaction-diffusion path length was identified to be a suitable parameter for product selectivity. An increase in the reaction-diffusion path results in an increase in -olefins re-adsorption, a decrease in olefin content and an increase branched product compounds. Secondary chain growth is not favoured under internal mass transport limitation.

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Pirola, C. "Novel Supported iron Fischer Tropsch catalysts : preparation, characterization and applications". Doctoral thesis, Università degli Studi di Milano, 2008. http://hdl.handle.net/2434/57056.

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For political and environmental concerns about fossil fuels, today it is imperative to develop economical and energy-efficient processes for the sustainable production of fuels and chemicals. Fischer Tropsch synthesis is a well-established industrial process able to utilize for these objectives syngas (mixture of H2, CO, CO2) manufactured from CH4, coal or, as a new tendency, from biomass. In particular, for the utilization of syngas from biomass it is necessary to use iron-based catalysts. The PhD work has performed an optimization study of particular iron based supported catalysts loaded with high amount of iron, in order to obtain a new kind of Fischer Tropsch catalysts having good performance and great mechanical resistance. The research has dealt with different studies: the catalyst composition (concerning both the loading of iron on silica and the quantity of promoters), the catalysts activation procedure before the FT runs, the calculation of the catalysts activation energy, the influence of many parameters as the temperature and the pressure of the reactor, the composition of the feeding gas, the influence of the calcination temperature of the used catalysts. Moreover, a deep catalysts characterization has been made using different techniques (BET, TPR, SEM, TEM, IR, micro-Raman, XRD, ICP) to correlate the FT results with the catalysts properties. All the catalysts have been prepared using the impregnation method and in some case an innovative procedure with the help of Ultrasound (US) has been tested. Moreover a project of a new membrane reactor has been made, in collaboration with Genoa University, to increase at maximum the stability and the optimization of the process.

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Fiske, Thomas Haukli. "Correlation of Catalyst Morphology with Attrition Resistance and Catalytic Activity of Fischer-Tropsch Catalysts". Thesis, Norges teknisk-naturvitenskapelige universitet, Institutt for kjemisk prosessteknologi, 2013. http://urn.kb.se/resolve?urn=urn:nbn:no:ntnu:diva-22778.

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Three alumina based support materials for the Fischer-Tropsch synthesis (FTS) catalyst has been prepared and investigated. The three support materials were prepared in order to obtain different mechanical strengths, henceforth denoted weak, medium and strong support. Magnesium modified γ-alumina support material calcined at 950°C and 1050°C were prepared as the medium and strong support respectively, whereas the unmodified alumina was used as the weak support. The modified support materials were both prepared by the incipient wetness impregnation method to obtain 10 wt .% Mg. Several batches were prepared to gain enough material for the planned experiments.Each of the support materials were subject to one crushing process in order to try to alter the particle morphology. The chosen method was determined based on the results from the specialization project. In this project, one method gave a larger change in morphology than other methods. Therefore a ball mill was the method of choice. Unprocessed samples and samples subjected to the ball mill for the three different materials were tested for attrition in an attrition rig, and characterized in terms of morphology using a particle analyzer. The different fractions were also analyzed with respect to particle morphology using an environmental scanning electron microscope (ESEM). FTS catalysts with 12 wt. % Co and 0,5 wt. % Re were prepared from the weak and the medium support materials, both unprocessed and milled fractions, using the incipient wetness impregnation. These four catalyst samples were tested for dispersion using a chemisorption experiment, and for activity and selectivity using a dedicated setup. Results from the particle analyzer showed that the morphology had not been altered as much as expected. Most change in shape occurred for the medium strength support material, but the observed alteration was much less than observed for the same experiment in the specialization project. For the weaker and stronger support, only a slight change was observed, and for the strong support material this change was in the direction of rounder particles. This is probably due to the excellent mechanical strength of the strong support, which leads to grinding of the kinks and corners of the particles and not the breakage of whole particles to smaller and more uneven fragments. With such relative small differences in morphology between the unprocessed and the milled materials, correlations of morphology with other parameters are difficult to obtain. The same correlation as from the specialization project, with rounder particles having a higher attrition resistance, was observed. A slight degree of correlation was also found between particle morphology and dispersion, where more uneven particles gave a slightly higher value of cobalt dispersion.

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Kostas, John Nicholas. "Temperature-programmed studies of alkali-promoted Ni/SiO[subscript]2 catalysts". Diss., Georgia Institute of Technology, 1986. http://hdl.handle.net/1853/12909.

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Halfacre, Kyle Alan. "Synthesis of Liquid Fuels Over Carbon Nanotube Catalysts". OpenSIUC, 2012. https://opensiuc.lib.siu.edu/theses/907.

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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%).

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Hondow, Nicole S. "The synthesis of new heterogeneous Fischer-Tropsch catalysts : the incorporation of metal aggregates in mesoporous silicas". University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2008. http://theses.library.uwa.edu.au/adt-WU2008.0083.

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Transition metals have been extensively studied as catalysts, and certain metals are known to be highly selective and active for certain processes. It is possible to use metal clusters as models for reactions occurring at metal surfaces, but it is often found that in practical applications these complexes are unstable and break down. It is possible to support or stabilise a metal species on, or in, an inorganic framework, making heterogeneous catalysts. A study of metal cluster chemistry with mixed-donor phosphine ligands was conducted, with several new ruthenium complexes synthesised. The chemistry of metal-sulfur interactions is applicable to the removal of sulfur from crude oil, and in an investigation to this chemistry, the bifunctional ligand HSCH2CH2PPhH was added to ruthenium clusters (Chapter 2). The addition of this sulfur-phosphine ligand to the cluster [Ru3([mu]-dppm)(CO)10] produced the carbonyl substituted cluster [Ru3([mu]-dppm)(H)(CO)7(SCH2CH2PPhH)] and the bridged complex [Ru3([mu]-dppm)(H)(CO)8(SCH2CH2PPhH)Ru3([mu]-dppm)(CO)9], as well as recovery of the starting material. Further reactions with this ligand were examined with [Ru3(CO)12] and other complexes were synthesised with different clusters and ligands (Chapter 2). The M41S materials, MCM-41 and MCM-48, are well ordered porous materials with high surface areas (Chapter 3). The incorporation of three different types of metal species, metallosurfactants, metal clusters and nanoparticles, into these materials was examined in an attempt to make heterogeneous catalysts for the Fischer-Tropsch process. The success of this was studied using characterisation techniques such as powder X-ray diffraction, transmission electron microscopy and BET surface area measurements. Metallosurfactants containing either copper or cobalt were added directly to the synthesis of the porous materials in an attempt to incorporate the metals into the framework structure of the porous silica (Chapter 3). This resulted in well ordered iv porous materials, but the successful incorporation of the metal species was found to be dependent on several factors. Organometallic clusters containing metals such as copper, iron and ruthenium, with supporting carbonyl ligands, were added post-synthesis to MCM-41 and MCM-48 (Chapter 4). Various reaction conditions were examined in attempts to ensure small particle formation. The optimum incorporation of nanoparticles containing iron and platinum was found to occur when a suspension of pre-made and purified nanoparticles was added post-synthesis to the M41S materials (Chapter 4). These materials resulted in porous silicas with well dispersed, small metal particles. The optimum conditions for the calcination of these new materials were determined, in an attempt to remove the ligands and stabilisers and retain the small metal particle size (Chapter 5). Testing for the Fischer-Tropsch process was conducted in a fixed bed reactor through which a flow of synthesis gas containing carbon monoxide and hydrogen could pass over the material (Chapter 5). Analysis by gas chromatography showed that the major product produced by all materials tested was methane, but other hydrocarbons were produced in small amounts, including hexane.

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Rose, Amadeus [Verfasser]. "Nano-carbon supported cobalt catalysts in Fischer-Tropsch synthesis / Amadeus Rose". Aachen : Shaker, 2014. http://d-nb.info/105157269X/34.

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Swart, Jurie Christiaan Wessels. "A theoretical view on deactivation of cobalt-based Fischer-Tropsch catalysts". Doctoral thesis, University of Cape Town, 2008. http://hdl.handle.net/11427/5394.

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Walsh, Richard. "Fischer-Tropsch synthesis over SiO2, ZnO and MnO supported cobalt catalysts". Master's thesis, University of Cape Town, 1999. http://hdl.handle.net/11427/17953.

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Includes bibliography.
Silica is well known as a support for cobalt supported Fischer-Tropsch catalysts. Silica has a high surface area with an amorphous structure that promotes dispersion of the active cobalt phase over the support surface. This dispersion is vital in terms of catalyst performance and derives from the strength of interaction between the cobalt and the support. However, the stronger the metal support interaction, the greater is the loss of active cobalt through formation of cobalt support species that are hard to reduce. Consequently ZnO and MnO were evaluated in comparison to Si02 as supports for cobalt supported Fischer-Tropsch catalysts. The aim of the study was to characterise the interaction between cobalt and the three supports (Si02, ZnO and MnO) in terms of the cobalt reducibility as visualised using TPR, exposed cobalt surface area and cobalt dispersion as evaluated using hydrogen chemisorption, and catalytic performance under Fischer-Tropsch synthesis conditions.

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Sadeqzadeh, Majid. "Deactivation modeling of cobalt Fischer-Tropsch catalysts in different reactor configurations". Thesis, Lille 1, 2012. http://www.theses.fr/2012LIL10172/document.

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La désactivation reste un enjeu important lors de la synthèse Fischer-Tropsch, car il limite la vie des catalyseurs, ainsi que leurs productivités catalytiques. Elle peut être liée à certains mécanismes selon la littérature. Le frittage a été proposé comme la source principale de désactivation initiale, et avec le cokage comme phénomène responsable de la désactivation à long-terme dans ce travail. Le but de cette thèse est de développer les modèles mécanistiques capables de prédire le changement d’activité catalytique des catalyseurs FT à base de cobalt avec le temps. Dans la première étape, le changement des propriétés physico-chimiques des particules avec le temps est considéré. Un modèle de frittage est développé, qui inclut l’effet d’accélération de l’eau par formation d’une couche d’oxyde de cobalt à la surface. Ce mécanisme nous permet de lier l’agglomération des particules à certaines conditions opératoires, notamment le rapport molaire de H2O/H2. Nous avons aussi développé un mécanisme pour l’empoisonnement des sites catalytiques par dépôt de carbone pour la désactivation à long-terme. Ce mécanisme permet d’évaluer le changement de fraction des sites libres avec le temps, ainsi que les fractions molaires de CO, H2, et H2O.Ces deux modèles microscopiques sont ensuite intégrés dans les modèles des réacteurs à lit fixe et slurry pour coupler les propriétés des catalyseurs et l’activité catalytique. L’effet des conditions opératoires sur la taille des cristallites, la fraction des sites actifs et la conversion sont considérés. Les modèles sont ensuite employés dans les réacteurs de laboratoire pour s’accorder avec les résultats expérimentaux
Catalyst deactivation remains a major challenge in Fischer-Tropsch synthesis; as it reduces the catalyst lifetime as well as its productivity. Deactivation can be attributed to certain mechanisms according to the literature. Sintering is proposed in this work to be responsible for the initial deactivation whereas coking is suggested to be the main cause of long-term deactivation. The final objective of this thesis is to develop the mechanistic models which could predict the extent of catalyst deactivation with time. In the first step, the change in the catalyst physico-chemical properties with time on stream is considered. A three-step sintering model is proposed which involves the effect of water acceleration through the formation of surface cobalt oxide layer. This mechanism allows correlating the crystallites growth with certain operating conditions especially the H2O/H2 molar ratio inside the reactor. We have also developed a mechanism for the active site poisoning by carbon deposition for the long-term deactivation. This mechanism helps to evaluate the change in the active sites coverage with time as well the CO, H2, and H2O mole fractions. The two microscopic models are then integrated in the reactor models in order to correlate the change in the catalytic activity with the catalyst properties. We have developed the models dedicated to fixed bed and slurry reactors. The effect of operating conditions on the crystallite size, active sites fraction, and conversion is considered by the simulations. The models are then employed in the laboratory scale reactors to fit the experimental data and to optimize the deactivation constants

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Suárez, París Rodrigo. "Noble metal catalysts for the hydrocracking of FT waxes". Thesis, KTH, Skolan för kemivetenskap (CHE), 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-158477.

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Bifunctional catalysts consisting of palladium or platinum and supported on amorphous silica-alumina were prepared and tested in the hydrocracking of n-hexadecane, which is considered to be representative of n-paraffins in hydrocracker feeds. In addition to the evaluation of the physicochemical properties, a comprehensive study on catalyst activity and selectivity has been conducted, in the full range of conversions. A theoretical model was proposed to fit the experimental conversion-selectivity data. The n-hexadecane reactivity pattern was expressed in terms of a reaction network involving lumps consisting of monobranched and multibranched n-hexadecane isomers, and cracking products. Pseudo first order kinetics and irreversible reaction steps were assumed in order to obtain the kinetic constants of each step. For the same metallic molar loading, a platinum-based catalyst proved more active than a palladium one. The reaction network model showed that cracking products were produced by means of a bifunctional mechanism on palladium catalysts, with n-hexadecane isomers as intermediates. However, on platinum catalysts, an additional monofunctional mechanism was observed. The noble metal catalyzes the hydrogenolysis of n-hexadecane without requiring any acid function. An increase in the platinum loading leads to an increase in the importance of this direct cracking route. The deactivation in the platinum-based catalysts is only due to coke formation, which deactivates the metal sites. The regeneration by means of a Temperature-Programmed Oxidation does not lead to a complete recovery of the metal function, according to the volumetric chemisorption measurements and the experimental selectivity data. Further work is required to determine the real causes.

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Nguyen, Tuan Huy Chemical Sciences &amp Engineering Faculty of Engineering UNSW. "Semiconductor oxide supported Mo and Mo-W carbide catalysts for Fischer-Tropsch synthesis". Awarded by:University of New South Wales. School of Chemical Sciences and Engineering, 2006. http://handle.unsw.edu.au/1959.4/26969.

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Fischer-Tropsch synthesis reaction to produce sulphur free hydrocarbons has enjoyed a resurgent in interests due to increases in world oil prices. In this work, the suitability of Mo and Mo-W carbides has been investigated as a possible cost-effective alternative to noble metals in Fischer-Tropsch synthesis. The molybdenum and tungsten monometallic and bimetallic carbides were prepared through precipitation from homogeneous solution to the sulphide followed by carburization with a mixture of propane and hydrogen to produce the resulting metal carbide. A 23 factorial design strategy was employed to investigate the effect of three carburizing variables, namely, time, temperature and gas ratio on the resulting catalyst. In particular, the effect of supports was also examined through four common semiconductor oxide supports, namely: Al2O3, SiO2, TiO2 and ZrO2. Thermogravimetric analysis of the carburization reactions showed that the conversion from metal sulphide to the metal carbides is a multistep process producing different phases of carbides, namely ??-MoC1-x, ??-Mo2C, ?? -WC1-x and ??-W2C, depending on heating rate and temperature. The rate determining step of the carburising reaction is the diffusion of carbon atoms into the metal matrix, hence giving relatively low activation energy values. Statistical analysis of the factorial design revealed that all three carburizing variables affect the final physiochemical makeup of the catalyst. SEM analysis showed that the carbides are well dispersed on the surface of the support and catalyst particles produced are nanoparticles in the range of 25 to 220 nm depending on the support. Fischer-Tropsch activity test showed that monometallic molybdenum carbide is active under Fischer-Tropsch conditions while tungsten carbide is inactive for the conditions studied in this project. However, bimetallic carbide catalyst, consisting of the two mentioned metals gave overall higher reaction rates and decreased methane selectivity. Steady state analysis revealed that there are two active sites on the surface of molybdenum carbide catalyst resulting in two chain growth propagation values when analysed via the Anderson-Schulz-Flory kinetics. Overall, ZrO2 support appeared to be the most suitable support followed by SiO2, TiO2 and Al2O3. Finally, kinetic modelling of data showed that methanation and higher hydrocarbons formation path occurs via combination of the oxygenated intermediate and Eley-Rideal mechanism.

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Peña, Zapata Diego. "Identification of deactivation mechanisms of cobalt Fischer-Tropsch catalysts in slurry reactor". Thesis, Lille 1, 2013. http://www.theses.fr/2013LIL10149/document.

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La synthèse Fischer -Tropsch (SFT) produit des carburants liquides ultra-propres, ainsi que des produits chimiques à partir du gaz de synthèse issu d’une large gamme de matières premières : gaz naturel, gaz de schiste, charbon, biomasse. Les catalyseurs supportés à base de cobalt sont la meilleure option pour la SFT à basse température, en raison de leur grande stabilité et leur sélectivité en hydrocarbures lourds. Néanmoins, ces catalyseurs se désactivent avec le temps au cours de la réaction. La désactivation réduit la durée de vie et la productivité de ces catalyseurs. Par conséquent, la désactivation reste un défi majeur de la SFT. Dans ce travail, nous avons identifié les mécanismes les plus pertinents de la désactivation du catalyseur à base de cobalt dans le réacteur slurry : frittage du cobalt, attrition du catalyseur et dépôt de carbone. Il est démontré que la vitesse de désactivation dépend des conditions opératoires. Les résultats expérimentaux suggèrent que l'attrition du catalyseur est fortement influencée par la pression partielle d’eau dans le réacteur. La pression partielle élevée d’eau favorise la mobilité des nanoparticules de cobalt à la surface et leur frittage. Des agglomérats de cobalt de quelques microns situés sur des grains de catalyseur, ainsi que des particules métalliques de cobalt individuelles ont été observés dans les catalyseurs usés. La formation des agglomérats de cobalt a été favorisée à des vitesses spatiales basses et dans le gaz de synthèse pauvre en hydrogène. La dilution du gaz de synthèse au début de la réaction diminue l’attrition et réduit la formation des agglomérats de cobalt. Des hydrocarbures, des alcools, des cétones, des aldéhydes, des acides organiques ont été détectés dans les catalyseurs usés ; α -oléfines étant les espèces les plus abondantes. Les acides carboxyliques et les aldéhydes cinnamiques semblent être le plus néfastes pour les performances catalytiques. Le schéma de la formation de différentes espèces de carbone à la surface des catalyseurs de cobalt dans le réacteur slurry été proposé dans le manuscrit
The Fischer-Tropsch Synthesis (FTS) produces ultra-clean liquid fuels and chemicals via conversion of syngas from a wide range of feedstocks: natural gas, shale gas coal and biomass. Supported cobalt-based catalysts are the best option for the low temperature FTS, due to their high stability and selectivity toward heavy paraffinic hydrocarbons. Nevertheless, cobalt catalysts deactivate with time on stream. This leads to a decrease in catalyst lifetime and productivity. Hence, catalyst deactivation remains a major challenge of FTS. In this work we identified cobalt sintering, catalyst attrition and carbon deposition as the most relevant catalyst deactivation mechanisms in slurry reactor; the deactivation rate being influenced by the operating conditions. The experimental results suggest that catalyst attrition is strongly affected by water partial pressure in the catalytic reactor. High water partial pressure favours mobility of cobalt nanoparticles on surface and cobalt sintering. Both cobalt agglomerates of micron size located on catalyst grains and detached cobalt metal particles were observed in the spent catalysts. The formation of cobalt agglomerates was favoured at lower gas space velocity and in H2-deficient syngas. Syngas dilution at the beginning of reaction decreases the degree of attrition and reduces cobalt agglomerate formation. Hydrocarbons, alcohols, ketones, aldehydes, organic acids were detected in the spent catalysts; α-olefins being the most abundant species. Carboxylic acids and alpha-alkyl cinnamic aldehyde seem to be most detrimental for the catalytic performance. A tentative schema of formation of different carbon species in cobalt catalysts during FTS in slurry reactor has been proposed in the manuscript

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Atubi, Phylander Omosigho. "Novel synthesis of silica-supported Fischer-Tropsch catalysts for second generation biofuels". Thesis, University of Huddersfield, 2015. http://eprints.hud.ac.uk/id/eprint/26187/.

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The objective of this study is to improve the catalytic performance of silica-supported Fischer-Tropsch cobalt based catalyst. Iron and nickel catalyst were also briefly studied. Initial work focused on synthesis of porous silica via oxidative thermal decomposition of polydimethylsiloxane (PDMS) and its characterisation. It was shown that PDMS undergoes at least two thermal degradation steps to form silica powder. It was also demonstrated that increase in isothermal time at constant temperature and increase in temperature at constant time could be used to tune the surface area and pore volume of the synthesized silica powder. Subsequently, a novel one pot technique called the swelling in method (SIM) was developed, and employed to synthesize silica-supported cobalt, iron and nickel based Fischer-Tropsch catalyst. The results of silica-supported cobalt based catalyst prepared by the swelling in method were compared with those synthesized by incipient wet impregnation method. The colloidal method was also combined with the swelling in method to prepare silica-supported cobalt nanoparticles catalyst. Characterisation of cobalt, iron and nickel based catalyst prepared by the swelling in method showed that PDMS as the initial catalyst support converted to silica powder after oxidative calcination. Physicochemical properties of silica-supported cobalt, iron and nickel catalyst prepared by the swelling in method suggest that the oxides of each metal were present inside the silica pores while cobalt based catalyst prepared by the same method had better surface area and pore volume compared to the catalyst synthesized by the incipient wetness impregnation technique. Catalytic performance of the catalyst synthesized by the swelling in and incipient wetness methods were studied in High Temperature Fischer-Tropsch synthesis reaction condition. The results showed that silica-supported cobalt based catalyst prepared by the swelling in method was overall more active, generated less methane and less susceptible to deactivation by sintering and carbon deposition when compared to the catalyst prepared by the impregnation technique. Silica-supported cobalt nanoparticles catalyst had the best catalytic activity in comparison to all the catalyst studied in this work. Silica-supported cobalt based catalyst prepared by the swelling in method using cobalt nitrate exhibited the best catalytic activity while the catalyst synthesized from cobalt acetate had the least activity. The addition of ruthenium to silica-supported cobalt catalyst contributed in minimising the formation of methane when compared to the catalyst without ruthenium. Silica-supported iron and nickel based catalyst showed reasonable catalytic activity, and as expected the amount of methane generated by nickel catalyst was relatively very high compared to all the catalyst studied in this thesis.

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Regali, Francesco. "Hydroconversion of model Fischer‑Tropsch wax over noble metal/silica-alumina catalysts". Doctoral thesis, KTH, Kemisk teknologi, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-129968.

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Synthetic fuels produced using the Fischer-Tropsch technology will play an important role in the future of the transportation sector. The Fischer-Tropsch synthesis (FTS) allows converting synthesis gas (CO + H2) into fuels of outstanding quality. The synthesis gas can be obtained from different carbon sources: natural gas, coal and biomass. In order to maximize the yield of middle distillates, the process is carried out in two main steps: the FT-synthesis that produces long-chain hydrocarbons (waxes) and a hydrocracking step, to selectively convert the waxes into fuels. Diesel produced by this process is characterized by excellent combustion properties and reduced harmful tailpipe emissions compared to conventional diesel. Due to the growing interest in synthetic fuel production, from the industry and the academia, and to the peculiar characteristics of the Fischer-Tropsch products, research in hydrocracking has received renewed attention. Catalysts for the hydrocracking of long-chain paraffins have been the subject of the present work, which is the summary of four scientific publications. Noble metals supported on acid carriers have been compared, especially for what regards the mechanisms through which hydrocracking proceeds. The catalysts were synthesized and characterized by various techniques, including N2 physisorption, H2 chemisorption, TEM, pyridine adsorption FTIR, ammonia TPD, etc. It was shown that catalytic activity is mainly dependent on the acid support used; that selectivity is strongly dependent on conversion, high conversion favoring highly branched cracking products. Two main reaction routes were observed: bifunctional hydrocracking and hydrogenolytic cracking. Platinum-containing catalysts showed high selectivity towards the latter, while palladium/silica-alumina behaved as pure bifunctional catalysts. Catalyst deactivation was investigated and initial sintering of metal particles was observed. Coking was also a cause of deactivation. Formation of coke deposits was highly dependent on the metal loading of the catalysts. Metal loading also influenced catalyst selectivity, especially in the case of platinum/silica-alumina catalysts. Monofunctional hydrogenolysis on the platinum particles, superimposed to the bifunctional mechanism was observed. This route increased selectivity towards linear hydrocarbons and methane, with increasing amounts of platinum. The specific rate of hydrogenolysis was constant for different loadings of platinum on the same acid silica-alumina support. Using a different, less acid, support negatively affected the hydrogenolytic activity of the platinum catalytic sites. It was concluded that metal-support interactions might play an important role in the catalytic properties of platinum surfaces. This work has contributed to increasing the knowledge about hydrocracking of long-chain alkanes and pointed out some features that might have practical interest in the application of this technology to synthetic-fuel production.
Syntetiska drivmedel tillverkade genom Fischer-Tropsch teknologin kommer i framtiden att ha en betydande roll för transportsektorn. Fischer-Tropsch syntesen (FTS) möjliggör omvandling av syntesgas (CO + H2) till högkvalitativa bränslen. Syntesgasen kan erhållas från olika kolkällor: naturgas, kol och biomassa. För att maximera utbytet av medeldestillat, utförs processen i två huvudsteg: FT-syntes som producerar långa kolväten (vaxer) och ett hydrokrackning steg, för att selektivt omvandla vaxerna till bränslen. Diesel som produceras med denna process kännetecknas av utmärkta förbränningsegenskaper och ger upphov till minskade utsläpp av skadliga ämnen jämfört med vanlig diesel. På grund av det växande intresset för syntetiska bränslen, både från industrin och den akademiska världen, och av de speciella egenskaperna hos Fischer-Tropsch-produkter, har forskningen i vätekrackning fått förnyad uppmärksamhet. Ämnet för detta arbete, som är en sammanfattning av fyra vetenskapliga publikationer, är katalysatorer för hydrokrackning av långkedjiga paraffiner. Ädelmetaller uppburna på sura bärare har jämförts, särskilt vad gäller vätekrackningsmekanismer. Katalysatorerna preparerades och karaktäriserades med hjälp av olika tekniker, bland andra N2 fysisorption, H2 kemisorption, TEM, pyridin adsorption FTIR, ammoniak TPD, etc. Det visade sig att den katalytiska aktiviteten är främst beroende av surheten hos bärarmaterialet, att selektivitet är starkt beroende av omsättningen, där hög omsättning gynnar flergrenade krackningsprodukter. Två huvudsakliga reaktionsvägar observerades: bifunktionell vätekrackning och hydrogenolytisk crackning. Platinakatalysatorer visade hög selektivitet mot det senare, medan katalysatorer med palladium på kiseloxid-aluminiumoxid uppträdde som rena bifunktionella katalysatorer. Katalysatordeaktivering undersöktes och sintring av metallpartiklar observerades. Koksning var också en orsak till deaktivering. Koksbildning var starkt beroende av metallhalten i katalysatorerna. Metallhalten påverkade också selektivitet, särskilt för platina-kiseloxid-aluminiumoxidkatalysatorer. Monofunktionellt hydrogenolys på platinapartiklarna, observerades utöver den bifunktionella mekanismen. Med denna reaktionsväg ökade selektivitet mot linjära kolväten och metan, med ökande platinahalter på katalysator. Den specifika reaktionshastigheten för hydrogenolys var konstant för olika platinahalter på en sur kiseloxid-aluminiumoxidbärare. Den hydrogenolytiska aktiviteten hos platina katalytiska säten påverkas negativt när en mindre sur bärare användes. Slutsatsen var att interaktioner mellan metallen och bäraren kan spela en viktig roll för de katalytiska egenskaperna hos platina ytor. Detta arbete har bidragit till att öka kunskapen om vätekrackning av långkedjiga alkaner och påpekade vissa funktioner som kan ha praktiskt intresse vid tillämpningen av denna teknik för produktionen av syntetiska bränslen.

QC 20131007

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Warringham, Robbie. "An investigation of iron-based Fischer-Tropsch catalysts using inelastic neutron scattering". Thesis, University of Glasgow, 2015. http://theses.gla.ac.uk/6364/.

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The primary objective of this study was to characterise standard iron based Fischer- Tropsch catalysts by using the hydrogenation of CO at elevated temperatures and ambient pressure as a test reaction. The reaction test data is supplemented by the following analytical techniques; X-ray diffraction (XRD), Raman scattering, temperature programmed oxidation (TPO), transmission electron microscopy (TEM) and also inelastic neutron scattering (INS). The aim of these studies is to characterise the hydrocarbonaceous species present on the catalyst surface after reaction and to propose what role these hydrocarbonaceous species may play in the Fe/CO/H2 surface chemistry; be it active or not. These initial characterisation studies of the reacted iron catalysts were then extended to study the temporal dependence of these species with increasing reaction time. The application of inelastic neutron scattering is shown to provide a great deal of information regarding the hydrocarbonaceous component present in these types of systems. Therefore the application of INS and the subsequent result constitute the majority of the discussion of this study. The research objectives for this study can be listed as follows; 1. To prepare an iron oxide catalyst using a reproducible and controlled method and to characterise this material using the methods outlined previously. 2. To react the iron oxide catalysts using a representative test reaction for the purpose of characterising the surface species present after reaction. 3. To use inelastic neutron scattering to probe and gain a vibrational spectroscopic insight to the hydrocarbonaceous species present. 4. To study the temporal dependence of the hydrocarbonaceous species and how they alter with increasing time-on-stream. The thesis will begin with an introduction to Fischer-Tropsch catalysis, with a focus on iron-based Fischer-Tropsch catalysis. The discussion will move to some heightened analysis of some previously reported INS measurements of iron Fischer-Tropsch catalysts. This prelude will be followed by the main discussion of results, that is the characterisation of the reacted iron oxide catalyst using inelastic neutron scattering and the temporal study with increasing time-on-stream. The thesis will then finish with a discussion on a brief study investigating the role of promoters in iron based Fischer-Tropsch catalysts, which constitutes future work.

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Barrientos, Javier. "Deactivation of cobalt and nickel catalysts in Fischer-Tropsch synthesis and methanation". Doctoral thesis, KTH, Kemisk teknologi, 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-190593.

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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.

QC 20160817

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Blignaut, Annalie. "Influence of basicity in Fischer-Tropsch synthesis over supported iron-based catalysts". Master's thesis, University of Cape Town, 2007. http://hdl.handle.net/11427/7477.

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Includes bibliographical references (leaves 115-124).
The Fischer-Tropsch synthesis catalyzed by iron is a well-established process for the production of synthetic fuels, waxes and high-value chemicals, such as α-olefins. A draw-back of the currently used iron-based catalysts is their short lifetime, caused by sintering and particle break-up. These disadvantages might be overcome by utilizing a supported iron-based catalyst. However, supported iron Fischer-Tropsch synthesis, which has been tested up to now, show a high methane selectivity. This might be caused by a lack of alkali near the catalytic site, which can be alleviated by using a basic support. Classical basic supports such as CaO and MgO will react with CO2 (a major by-product in iron-catalyzed Fischer-Tropsch synthesis) yielding carbonates and can therefore not be used, since the formation of carbonates will result in a large particle expansion. An alternative would be to generate a silica-based basic support by attaching basic groups to the silica. In this study iron Fischer-Tropsch catalysts supported on silica were tested for conversion of synthesis gas to hydrocarbon products. Silica was modified with aminopropyltriethoxysilane (APTeS) by impregnation followed by calcination to provide basic surface groups onto the silica surface. The CHN analysis and IR-analysis indicate the presence of amine groups in the APTeS-modified silica. The pore radius distribution of silica is slightly shifted towards higher pore radii in comparison to APTeS-modified silica. It might thus be stated that aminopropyltriethoxysilane covers the pore walls and does not seem to result in pore blockage. Thermal gravimetric analysis indicates that the thermal stability of APTeS-modified silica is low. A major difference between silica and APTeS-modified silica was their zeta-potential. Whereas the surface of silica is mainly negatively charged in the pH-range of interest during impregnation, the surface of APTeS-modified silica is mainly positively charged. This is attributed to the presence of amine groups on the surface. Iron was brought onto the support by impregnation. The surface modification of silica with APTeS seems to be destroyed upon calcination of the impregnated catalysts. The iron phase in the calcined iron catalyst supported on silica catalysts is mainly hematite (Fe203), whereas the iron phase in the calcined iron catalyst supported on APTeS-modified silica catalysts is mainly iron oxide hydroxide FeOOH. The presence of basic amine groups may favour the formation of FeOOH crystallites during the impregnation/calcination on the APTeS-modified silica. The FeOOH-crystallites on the APTeS-modified silica support are typically smaller than the Fe203 crystallites on silica. The maximum catalytic activity is obtained at 0.01 mol K I mol Fe for the iron catalyst supported on silica and at 0.02 mol K I mol Fe for the APTeS-modified catalyst, indicating the optimum potassium loading. The difference in the optimum potassium loading might be linked to the smaller crystallite sizes obtained with the APTeS-modified catalyst. All the potassium promoted catalysts show a lower methane selectivity compared to the 0 K iron catalyst supported on silica and the 0 K iron catalyst supported on APTeS-modified silica. The 1-olefin and n-olefin content in the fraction of linear hydrocarbons increase with increasing potassium loading over all the iron catalyst supported on silica promoted with potassium except for the catalysts 0.005 K and 0.01 K. Increasing potassium content on the catalyst resulted in higher 1-olefin content in the fraction of linear olefins. The trend suggests that potassium promotion suppresses secondary double bond isomerisation of 1-0lefin into internal olefins. The high degree of branching obtained with the 0.005 K catalyst and the 0.01 K catalyst, is characteristic of weak alkali promotion. The iron catalysts supported on APTeS-modified silica indicate an increase in the degree of branching with increasing potassium content.

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Wigzell, Fiona A. "Characterising the activation process for cobalt catalysts used in Fischer-Tropsch synthesis". Thesis, University of Glasgow, 2012. http://theses.gla.ac.uk/3753/.

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The effects of precursor, support and calcination procedure on the physical and chemical properties of supported cobalt catalysts have been investigated. A multiple characterisation approach of thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction and transmission electron microscopy was employed in order to gain understanding into the calcination and reduction processes. In addition, the catalysts were screened on a purpose built fixed bed reactor, under industrially relevant conditions, to determine effect of catalyst preparation on Fischer-Tropsch activity.

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35

Lu, Mengnan. "New technology development for advanced "Clean" solid catalysts for Fischer-Tropsch synthesis". Thesis, Lille 1, 2015. http://www.theses.fr/2015LIL10108.

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La synthèse Fischer-Tropsch (FT) convertit le gaz de synthèse en hydrocarbures liquides avec le catalyseur au cobalt pour les nouveaux carburants alternatifs ultrapropres. Les catalyseurs pour la synthèse FT sont actuellement préparés par des moyens chimiques comme l'imprégnation etc. Toutes ces voies impliquent des solvants toxiques et retraitement à haute température. En raison du coût plus faible, d’une réduction des besoins en énergie et de la pollution de l'environnement, la mécano-chimique a un certain nombre d'avantages pour la synthèse de la catalyse hétérogène par rapport à des techniques classiques. Dans cette thèse, la méthode mécano-chimique a été utilisé pour préparer des catalyseurs au cobalt supportés par l’alumine, pour la synthèse FT. Contrairement à la préparation de catalyseur classique, le dépôt de phase active ne comportait aucun solvant. Le but de ce travail est d'obtenir des catalyseurs efficaces FT et de simplifier la synthèse de catalyseur en réduisant le nombre d'étapes de préparation. Le projet consiste par une méthode innovante de synthèse de catalyseurs en trois processus de travail mécaniques différents dans le contexte sec. Le processus mécano-chimique pour synthétiser le catalyseur pour la réaction FT a été développé. Les conditions de la technique de revêtement ont été identifiés par l'étude des conditions optimales. En outre, les caractérisations ont été étudiées pour comprendre les mécanismes derrière le dépôt de particules sur l’interface. Les tests de performances catalytiques ont été estimés dans un réacteur à lit mili-fixé; un algorithme d'optimisation des paramètres dans un processus mécanique a été réalisé par l'intermédiaire dérivant la formule cible sur l'énergie
Fischer–Tropsch (FT) synthesis converts syngas into liquid hydrocarbons over cobalt catalyst for new ultraclean alternative fuels. The syngas can be produced from both fossil and renewable resources. The catalysts for FT synthesis are currently prepared by chemical ways like impregnation etc. All these routes involve toxic solvents and high temperature retreatment. Because of lower cost, reduced energy requirements and environmental pollution, the mechano-chemistry has a number of advantages for the synthesis of heterogeneous catalysis compared to conventional techniques. In this study, the mechano-chemical method was used to prepare alumina supported cobalt catalysts for FT synthesis. Differently to the conventional catalyst preparation, the deposition of active phase did not involve any solvent in the proposed method. The goal of this work is to obtain efficient FT catalysts and to simplify catalyst synthesis by reducing the number of preparation steps. The project involves innovative method of synthesis of catalysts in three different mechanical working processes in dry context. The process of mechano-chemistry to synthesize the catalyst for FT reaction was developed. The operating conditions for the control of the coating technique were identified through optimal conditions study by statistical analysis. Moreover, characterizations were studied to understand the basic mechanisms behind deposition of particles on the interface. Catalytic performance tests were estimated in a mili-fixed bed reactor; Optimization algorithm of parameters in a mechanical process was carried out via deriving target formula about energy and material size

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Liu, Chang. "Effect of sulphur on Fischer-Tropsch synthesis : promoted molybdenum and cobalt catalysts". Thesis, Lille 1, 2015. http://www.theses.fr/2015LIL10134/document.

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Cette thèse porte sur l’étude de catalyseurs promus à base de sulfure de molybdène supporté sur alumine ou nanotubes de carbone pour la synthèse d’oléfines à partir du gaz de synthèse issu de la biomasse. Les catalyseurs ont été étudiés à chaque étape de leur préparation par différentes techniques physico-chimiques et spectroscopiques et testés dans un réacteur à lit fixe. Les résultats ont montré que deux types de sites sont présents sur les catalyseurs K-MoS2 : MoS2, qui conduit à la production de méthane et une phase mixte K-Mo-S qui conduit à la synthèse d’oléfines. La baisse d’activité observée avec les catalyseurs supportés sur nanotubes de carbone a été attribuée au plus faible taux de sulfuration. La basicité des promoteurs et la taille des cristallites sont des paramètres importants qui influencent la synthèse d’oléfines. Une basicité modérée ainsi qu’une taille plus grande des cristallites de molybdène sont favorables à la synthèse d’oléfines légères
This thesis focuses on the study of promoted molybdenum catalysts supported on alumina or carbon nanotubes for the synthesis of olefins from synthesis gas obtained from biomass. The catalysts were studied at every stage of their preparation by different characterization techniques and tested in fixed bed reactor. The results showed that both types of sites are present on the K-MoS2 catalysts: MoS2, which leads to the production of methane and a mixed K-Mo-S phase which leads to the synthesis of olefins. The decrease in activity observed with catalysts supported on carbon nanotubes was attributed to the low rate of sulphidation. The basicity of the promoters and the size of the molybdenum sulphide crystallites are important parameters influencing the olefins synthesis. A moderate basicity as well as large size of molybdenum crystallites are favorable to the synthesis of light olefins

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Coombes, Matthew. "The effect of silica on the reduction of precipitated iron-based fischer-tropsch catalysts". Thesis, Nelson Mandela Metropolitan University, 2016. http://hdl.handle.net/10948/14873.

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Iron Fischer-Tropsch (FT) catalysts are typically prepared as iron oxides which are reduced to FT-active iron metal and iron carbide prior to FT synthesis. The iron oxides contain a variety of diﬀerent chemical and structural promoters to alter FT-activity. Silica is a common structural promoter which stabilises the formation of small crystallites and provides mechanical integrity to the catalyst. However, silica inhibits the reduction of the oxide precursor to the FT-active phases. This ultimately aﬀects catalyst activity and product selectivity. It has been proposed that the silica interacts with the iron to form encapsulating shells of fayalite (Fe2SiO4), or fayalite rafts between the iron oxide and the silica support. In this study, six silica-promoted iron oxide samples were prepared using a simple co-precipitation technique. Samples contain varying amounts of silica, and the samples are named 100/x Fe/SiO2, where x is the weight of silica for 100 weight iron, with x taking on values of 0, 10, 25, 50, 100 and 200. The resulting iron oxides were characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diﬀraction (XRPD), M¨ossbauer spectroscopy (MS), magnetic susceptibility measurements (MM), Raman spectroscopy, thermal gravimetric analysis (TGA) and nitrogen physisorption. Their reduction in a hydrogen atmosphere was investigated using temperature programmed reduction (TPR), in situ XRPD and TEM. The reduction in hydrogen of 100/0 Fe/SiO2 and 100/10 Fe/SiO2 was also studied using in situ gas ﬂow TEM cells. These cells allow the samples to be studied in the electron microscope at temperature and pressure conditions approaching those experienced in a real reactor environment. In the absence of a silica promoter (100/0 Fe/SiO2), hematite particles are formed with mean particle diameters of 39 ± 12 and 52.7 ± 0.2 nm determined using TEM and XRPD respectively. MM data reveals a magnetic transition (Morin transition) at≈230 K, consistent with a mean particle size of≈50 nm. In a hydrogen atmosphere, the hematite reduces to metallic iron via a two-step process viz. hematite → magnetite → iron. The ﬁnal iron particles have an average crystallite size of 68.0 ± 0.2 nm. The presence of lower amounts of silica in the samples 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 results in the formation of silicasubstituted 2-line ferrihydrite particles. Bands in the Raman spectra of these samples shift on increasing silica content, which indicates an increasing number of Fe-O-Si bonds within the ferrihydrite framework. MM reveals typical superparamagnetic (SPM) behaviour above a blocking temperature in the range 39 - 68 K which gives mean particle sizes of 4.2, 3.6 and 3.5 nm for 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 respectively, in good agreement with particle sizes determined using TEM (3.1±0.4, 2.4±0.3 and 2.4±0.3 nm respectively). MS data at 300 K and 4.2 K were ﬁtted with distributions of ∆EQ and Bhf respectively. The median values of Bhf decrease with increasing silica content, indicating greater degrees of distortion in the Fe3+ environments induced by increased silica substitution. The reduction to metallic iron occurs via a three-step process viz. hematite → magnetite → wu¨stite → iron, with the silica stabilising the wu¨stite phase. The increasing amount of Fe-O-Si bonds on increasing silica content shifts reduction to higher temperatures broadens each reduction step as a result of local Fe-O-Si concentration variations. Fractions of each sample are not completely reduced even at 1000°C, with the relative proportion increasing with increasing silica content. In situ gas ﬂow TEM studies reveal that the mechanism of reduction involves the liberation of atomic iron atoms from the silica-substituted iron oxides which agglomerate and grow into ﬁnal iron particles. This leaves a poorly crystalline Fe-O-Si bonded framework behind. STEM-EDS and STEM-EELS reveal low concentrations of silicon at the surface of the resulting iron particles, however they do not form encapsulating shells of fayalite as previously suggested. The majority of the silica remains in the Fe-O-Si material which may crystallise into separate fayalite particles at elevated temperature. The presence of silica in high proportions (100/100 Fe/SiO2 and 100/200 Fe/SiO2) results in the formation of a two-phase system consisting of silicasubstituted 2-line ferrihydrite particles which are encapsulated in an ironinfused amorphous silica network. As with the other silica-bearing samples, there is an increase in Fe-O-Si bonds and an increase in the degree of distortion at Fe3+ sites with increasing silica content. The large amount of silica suppresses the blocking temperature of the SPM crystallites. In a hydrogen atmosphere, the reduction to metallic iron follows the same three step process as the other silica-bearing samples. Reduction temperatures are further shifted to higher values and given reduction steps are considerably broader with increasing silica content. The fraction of iron not fully reduced also increases. Iron particle diameters are very small, since encapsulation by the silica matrix prevents growth of particles.

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Schweicher, Julien. "Kinetic and mechanistic studies of CO hydrogenation over cobalt-based catalysts". Doctoral thesis, Universite Libre de Bruxelles, 2010. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/210036.

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During this PhD thesis, cobalt (Co) catalysts have been prepared, characterized and studied in the carbon monoxide hydrogenation (CO+H2) reaction (also known as “Fischer-Tropsch” (FT) reaction). In industry, the FT synthesis aims at producing long chain hydrocarbons such as gasoline or diesel fuels. The interest is that the reactants (CO and H2) are obtained from other carbonaceous sources than crude oil: natural gas, coal, biomass or even petroleum residues. As it is well known that the worldwide crude oil reserves will be depleted in a few decades, the FT reaction represents an attractive alternative for the production of various fuels. Moreover, this reaction can also be used to produce high value specialty chemicals (long chain alcohols, light olefins…).

Two different types of catalysts have been investigated during this thesis: cobalt with magnesia used as support or dispersant (Co/MgO) and cobalt with silica used as support (Co/SiO2). Each catalyst from the first class is prepared by precipitation of a mixed Co/Mg oxalate in acetone. This coprecipitation is followed by a thermal decomposition under reductive atmosphere leading to a mixed Co/MgO catalyst. On the other hand, Co/SiO2 catalysts are prepared by impregnation of a commercial silica support with a chloroform solution containing Co nanoparticles. This impregnation is then followed by a thermal activation under reductive atmosphere.

The mixed Co/Mg oxalates and the resulting Co/MgO catalysts have been extensively characterized in order to gain a better understanding of the composition, the structure and the morphology of these materials: thermal treatments under reductive and inert atmospheres (followed by MS, DRIFTS, TGA and DTA), BET surface area measurements, XRD and electron microscopy studies have been performed. Moreover, an original in situ technique for measuring the H2 chemisorption surface area of catalysts has been developed and used over our catalysts.

The performances of the Co/MgO and Co/SiO2 catalysts have then been evaluated in the CO+H2 reaction at atmospheric pressure. Chemical Transient Kinetics (CTK) experiments have been carried out in order to obtain information about the reaction kinetics and mechanism and the nature of the catalyst active surface under reaction conditions. The influence of several experimental parameters (temperature, H2 and CO partial pressures, total volumetric flow rate) and the effect of passivation are also discussed with regard to the catalyst behavior.

Our results indicate that the FT active surface of Co/MgO 10/1 (molar ratio) is entirely covered by carbon, oxygen and hydrogen atoms, most probably associated as surface complexes (possibly formate species). Thus, this active surface does not present the properties of a metallic Co surface (this has been proved by performing original experiments consisting in switching from the CO+H2 reaction to the propane hydrogenolysis reaction (C3H8+H2) which is sensitive to the metallic nature of the catalyst). CTK experiments have also shown that gaseous CO is the monomer responsible for chain lengthening in the FT reaction (and not any CHx surface intermediates as commonly believed). Moreover, CO chemisorption has been found to be irreversible under reaction conditions.

The CTK results obtained over Co/SiO2 are quite different and do not permit to draw sharp conclusions concerning the FT reaction mechanism. More detailed studies would have to be carried out over these samples.

Finally, Co/MgO catalysts have also been studied on a combined DRIFTS/MS experimental set-up in Belfast. CTK and Steady-State Isotopic Transient Kinetic Analysis (SSITKA) experiments have been carried out. While formate and methylene (CH2) groups have been detected by DRIFTS during the FT reaction, the results indicate that these species play no role as active intermediates. These formates are most probably located on MgO or at the Co/MgO interface, while methylene groups stand for skeleton CH2 in either hydrocarbon or carboxylate. Unfortunately, formate/methylene species have not been detected by DRIFTS over pure Co catalyst without MgO, because of the full signal absorption.

Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

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Hubble, Ross. "Studies of carbon dioxide methanation and related phenomena in porous catalysts". Thesis, University of Cambridge, 2019. https://www.repository.cam.ac.uk/handle/1810/286588.

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This Dissertation investigates the kinetics of CO2 methanation over nickel and cobalt catalysts. Methanation was studied for both Ni/γ-Al2O3 and Co/ZrO2 catalysts, which were synthesised using an incipient wetness impregnation technique and subsequently characterised using analyses based on gas adsorption, XRD, TPR and thermogravimetry. Separately a CO hydrogenation reaction, the Fischer-Tropsch process, was modelled numerically to examine the influence of mass transfer in practical, commercial pellets of catalyst. The kinetics of methanation was investigated for Ni/γ-Al2O3 over a wide range of reactant partial pressures using a gradientless, spinning-basket reactor operated in batch mode and in a laboratory-scale, continuous fixed-bed reactor. Langmuir-Hinshelwood kinetic models were developed to represent the observed kinetics in each reactor: these models were then compared. For the batch reactor, a rate expression based the dissociation of a chemisorbed CO intermediate being the rate-limiting step was found to be consistent with the experimental results. However, results from the fixed-bed suggested that the hydrogenation of an adsorbed C atom determined the rate of reaction. These differences in the kinetics on Ni/γ-Al2O3 between the fixed-bed and batch reactors suggest that a Langmuir approach using a single, rate-determining step may not be representative across all conversions. The rate over the Co/ZrO2 catalyst was characterised in the fixed-bed reactor over a range of reactant partial pressures at temperatures between 433 K and 503 K. The rate was observed to be dependent on hydrogen partial pressure and temperature, with the rate increasing with both. Previous research has reported a wide range of values of the apparent activation energy, with a study suggesting it was sensitive to pressure. Accordingly, the apparent activation energy was investigated for pressure sensitivity over a range of pressures between 5 and 15 barg: it was found to be constant. The values determined (~88-91±8 kJ/mol) were notably consistent with those reported for CO hydrogenation on cobalt. Kinetic schemes based on Langmuir-Hinshelwood and power law equations were evaluated, with the results best described by a reaction scheme based on the carbide pathway, with a rate-determining step of CH hydrogenation. A reaction-diffusion model of the Fischer-Tropsch process in a 2-D hollow cylinder was developed and analysed across a range of Thiele moduli and the extents of error in both effectiveness factor and selectivity were quantified relative to one-dimensional sphere and slab analogues. The errors between 2-D and 1-D analogues were found to be most significant between Thiele moduli of ~0.25 and ~3. Hollow cylinder effectiveness factors were bounded by those of sphere and slab above and below Thiele moduli of ~0.75 and ~1.15 respectively for the conditions examined, with the effectiveness factors exceeding those of both sphere and slab models between these moduli. A comparison of the hollow cylindrical pellets against spheres of equivalent volume demonstrated that hollow cylinders provided improved fixed-bed performance, with improved effectiveness factors and selectivities due to the lowered diffusion lengths of the hollow cylindrical geometry.

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Romar, H. (Henrik). "Biomass gasification and catalytic conversion of synthesis gas:characterisation of cobalt catalysts for Fischer-Tropsch synthesis". Doctoral thesis, Oulun yliopisto, 2015. http://urn.fi/urn:isbn:9789526208015.

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Abstract Biomass gasification as a thermochemical treatment method is typically used for heat and power production. Instead of burning the producer gas, it can be converted to added-value products, i.e to fuels and chemicals. One such conversion is the catalytic Fischer-Tropsch synthesis (FTS) which converts synthesis gas to a chain of aliphatic hydrocarbons (FT diesel) as studied in this thesis. This requires, however, proper cleaning steps of producer gas, such as the removal of tar compounds and other impurities. These cleaning steps are not considered in this thesis. The first goal of the thesis was to determine the tar content in the producer gas from a small scale biomass gasifier. This subject is discussed in Paper I. The second and main goal of the thesis was the preparation and characterization of cobalt (or iron) catalysts for catalytic conversion of a gas mixture close to the synthesis as discussed in Papers II-V. The overall aim of the second part was to study the effects of promoters on the reducibility of cobalt and the effects of different calcination conditions on the degree of reduction and size of the metallic cobalt particles. In this later part different catalytic supports were used. According to the results of the thesis, naphthalene and toluene were the main tar compounds in the producer gas representing almost 80 % of the GC detected tar compounds. Only traces of polycyclic aromatic compounds were detected and no phenolic compounds were found in the gas. Further, a number of supported heterogeneous catalysts for FTS using cobalt (Co) or in some cases iron (Fe) as the active metal were prepared and characterized. These catalysts were supported on alumina (Al2O3), titanium dioxide (TiO2) or silicon carbide (SiC). Catalysts were promoted with Ru, Re or Rh in the concentrations of 0, 0.2, 0.5, and 1.0 mass-%. Several characterization methods (such as H2-TPR, catalytic activity measurements, N2 physisorption, CO chemisorption, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD)) were used to find answers to the behaviour of these catalysts under selected conditions and in the model reaction of FTS. Based on the results, there are significant differences in the characteristics of the catalysts, the differences are dependent of the supports used, promoters added and calcination conditions used. The properties of the support, especially the pore size distribution will effect the distribution of products formed in the Fischer-Tropsch synthesis. Addition of promoters and variatons in calcination conditions will effect the dispersion and the particle size of the active metal
Tiivistelmä Biomassan kaasutus on termokemiallinen prosessi, jota käytetään pääosin sähkön- ja lämmöntuotannossa. Polton sijaan kaasutuksessa muodostuva synteesikaasu voidaan puhdistaa ja hyödyntää edelleen katalyyttisesti polttoaineiden ja kemikaalien valmistuksessa. Eräs mahdollisuus synteesikaasun hyödyntämiseen on Fischer-Tropsch synteesi (FTS), jossa koboltti- tai rautakatayyteillä voidaan tuottaa alifaattisia hiilivetyketjuja (FT-dieseliä), mitä on tutkittu tässä työssä. FT-synteesi vaatii kuitenkin puhtaan tuotekaasun ja sen vuoksi tervayhdisteet ja muut epäpuhtaudet on poistettava kaasusta. Kaasun puhdistusta ei ole kuitenkaan tutkittu tässä työssä. Työn ensimmäisenä tavoitteena oli määrittää biomassan kaasutuksessa käytettävän pienikokoisen myötävirtakaasuttimen kaasun koostumus ja tervayhdisteet ja niiden pitoisuudet (julkaisu I). Toisena, ja tämän työn päätavoitteena oli Fischer-Tropsch -synteesissä käytettävien koboltti- ja rautakatalyyttien valmistus ja karakterisointi sekä käyttö synteesikaasun katalyyttisessä konvertoinnissa (julkaisut II-V). Erityisesti tutkittiin promoottorimetallien ja kalsinointiolosuhteiden vaikutusta koboltin pelkistymiseen ja kobolttimetallipartikkelien kokoon. Lisäksi tutkittiin ja vertailtiin erilaisia tukiaineita. Työn tulosten perusteella naftaleiini ja tolueeni olivat pääasialliset tervayhdisteet myötävirtakaasuttimen tuotekaasussa ja niiden osuus oli yli 80 % kaasukromatografisesti havaittavista tervayhdisteistä. Lisäksi havaittiin pieniä määriä polysyklisiä aromaattisia yhdisteitä, kun taas fenolisia yhdisteitä ei havaittu tuotekaasussa. Työssä valmistettiin ja karakterisoitiin lukuisa määrä erilaisia FT-katalyyttejä, joissa aktiivisena metallina oli koboltti tai rauta. Katalyyteissä tukiaineena oli alumiinioksidi (Al2O3), titaanidioksidi (TiO2) tai piikarbidi (SiC) ja promoottorimetallina joko Ru, Re tai Rh (pitoisuudet 0, 0.2 tai 1.0 massa-%). Katalyyttien karakterisointiin käytettiin useita menetelmiä, kuten H2-TPR, N2-adsorptio, CO-kemisorptio, XPS, XRD ja lisäksi määritettiin katalyyttien aktiivisuus ja selektiivisyys valituissa olosuhteissa FT-synteesin mallireaktioissa. Tulosten perusteella katalyyttien välillä havaittiin selkeitä eroja riippuen käytetystä tukiaineesta, promoottorista ja kalsinointiolosuhteista. Tukiaineen ominaisuudet, erityisesti huokoskokojakauma vaikuttavat FT-synteesin tuotejakaumaan. Promoottorien lisäys katalyyttiin sekä kalsinointiolosuhteet vaikuttavat lisäksi dispersioon ja aktiivisen metallien partikkelikokoon

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Souza, Guilherme de. "Preparação, caracterização e desempenho de catalisadores à base de ferro na Síntese de Fischer-Tropsch". reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2010. http://hdl.handle.net/10183/26006.

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Neste trabalho, foram investigados diferentes catalisadores à base de ferro, desde aspectos relacionados à sua preparação e caracterização até o seu desempenho na Síntese de Fischer-Tropsch. A abordagem incluiu a preparação de diferentes grupos de catalisadores e o estudo do efeito da temperatura de reação, da influência de parâmetros de síntese e do efeito da adição de cobalto e cobre às amostras sobre o seu desempenho catalítico. Os testes foram conduzidos por 6 h em reator tubular de leito fixo, sob pressão de 0,18 MPa, em temperaturas entre 280 e 320°C, carga de 500 mg e vazão de alimentação de 10 mL.min-1 da mistura H2/CO (razão molar 2:1) diluída em 40 mL.min-1 de N2. Além de aumentar a atividade do catalisador, o aumento da temperatura da reação resultou em maior seletividade para CO2, maior razão olefina/parafina, maior formação de coque e menor tendência à formação de produtos mais pesados. Nas condições empregadas, observou-se que a adição de cobre a catalisadores Fe-Si aumenta a área específica e a atividade da reação, mas a tendência à desativação por deposição de coque é elevada e a distribuição dos produtos é prejudicada. Quanto aos parâmetros de síntese, o tempo de cristalização e o agente precipitante pouco influenciaram a performance dos catalisadores, mas esta foi comprometida pelo tratamento térmico em atmosfera estagnada. O estudo dos catalisadores Fe-Al e Mg-Fe mostrou que há uma elevação significativa da área específica e de sua atividade quando há adição de um terceiro metal (cobre e cobalto). Também se verificou um sensível deslocamento para formação de produtos com cadeias carbônicas mais longas e uma diminuição da seletividade a CO2. A ativação com H2 das amostras contendo Co e Cu resultou na sinterização destes metais, sendo o último o mais afetado devido à redução do cobre ocorrer em menor faixa de temperatura, conforme mostrado pelos perfis de TPR. Maiores teores de cobre prejudicaram tanto a seletividade como a atividade dos dois grupos de catalisadores. As amostras do grupo Fe-Al apresentaram distribuição de produtos mais interessante do que as do grupo Mg-Fe e maiores conversões de CO para as amostras auto-ativadas contendo Cu. No entanto, os catalisadores do grupo Fe-Al, por possuírem maior acidez, apresentaram maior tendência à desativação por deposição de coque. O catalisador do tipo Cu-Fe-Al submetido a ciclos de reação-regeneração consecutivos apresentou contínua perda de atividade, associada à sinterização e à oxidação incompleta do coque. O acompanhamento do sinal de O2 durante os ensaios de regeneração sugeriu uma deposição de coque mais pesado para regenerações mais recentes.
Aspects related to preparation, characterization and performance for Fischer- Tropsch synthesis of iron-based catalysts were investigated in this work. The approach included the preparation of different groups of catalysts and the study of the effect of reaction temperature, the influence of synthesis parameters and the effect of adding cobalt and copper to samples over its catalytic performance. Tests were performed for 6 h in a tubular fixed bed reactor on 0.18 MPa, temperature between 280 and 320°C, 500 mg of catalyst and H2/CO (2:1 molar ratio) with a flow rate of 10 mL.min-1 diluted to 40 mL.min-1 N2 stream. In addition to improving catalyst activity, the increase in reaction temperatures resulted in higher selectivity to CO2, higher olefin-to-paraffin ratio, higher coke formation and lower tendency to form heavier products. Under these reaction conditions, the addition of copper to Fe-Si catalysts increased the specific surface area and reaction activity, but enhanced the deactivation tendency due to coke formation and affected the products distribution. Evaluating the synthesis parameters, the crystallization time and the precipitating agent had little influence over catalyst performance, but it was affected by the agent had little influence over catalyst performance, but it was affected by the thermal treatment on stagnant atmosphere. The study of Fe-Al and Mg-Fe catalysts showed a significant increase in specific surface area and in activity when a third metal (copper and cobalt) is added. A significant shift in selectivity towards higher chain length products and a lower selectivity to CO2 were also verified. H2 activation step of Co and Cu-containing samples resulted in sintering of these metals. The effect of sintering appeared to be more severe for Cu-containing catalyst once copper reduces in lower temperature range, as shown in TPR profiles. The increase of copper content had a detrimental effect over selectivity and activity of both catalyst groups. The Fe-Al catalysts showed more interesting product spectra distribution compared to Mg-Fe ones, and showed higher CO conversion for self-activated Cucontaining catalysts. Nevertheless, the Fe-Al group catalysts showed higher deactivation tendency due to coke deposition as they presented stronger acidity. The Cu-Fe-Al type catalyst submitted to consecutive reaction-regeneration cycles showed a continuous loss of activity associated to sintering and incomplete coke oxidation. The monitoring of O2 signal during regeneration tests suggested the formation of a heavier coke for earlier regeneration.

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SILVA, JAQUELINE FARIAS DA. "CATALYSTS SUPPORTED IN MICRO AND MESOPOROUS MOLECULAR SIEVES FOR THE FISCHER- TROPSCH SYNTHESIS". PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2004. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=6221@1.

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CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
A síntese de Fischer-Tropsch converte o gás de síntese (H2 + CO), em uma variedade complexa de hidrocarbonetos na presença de um catalisador (principalmente Co/Al2O3). Neste trabalho foram estudados catalisadores de Co e o Fe (1 e 5% em massa), incorporados aos suportes: zeólitas KL, HL 0,1M e HL 1,0 M, além da peneira molecular mesoporosa MCM- 41, pelo método de impregnação úmida incipiente, para a reação de Fischer- Tropsch. As amostras preparadas foram analisadas pelas técnicas de: Espectometria de Emissão Atômica de Plasma Acoplado Induzido, Adsorção Física de N2 pelo método BET, Difração de Raios-X, Redução com Temperatura Programada, Microscopia Eletrônica de Transmissão (MET), Quimissorção de Hidrogênio e Espectroscopia no Infravermelho de piridina adsorvida. Além disso, as amostras foram avaliadas em um reator de leito fixo na reação de Fischer-Tropsch. Para as amostras de ferro, com mesmo teor e suportes diferentes, pode-se observar que a amostra suportada na MCM-41 apresentou um grau de redução menor. Entre as amostras de ferro suportadas na KL, a 5% Fe/KL apresentou maior grau de redução e foi observado por microscopia eletrônica de transmissão (MET) que as partículas de ferro apresentaram diâmetro em torno de 6 nm. Para as amostras de cobalto foi observado que a temperatura de redução da amostra suportada na MCM-41 foi mais alta. A amostra 5% Co/KL apresentou um maior grau de redução. Foi possível observar por MET que as partículas de cobalto apresentaram diâmetro variando entre 8 e 20 nm. Verificou-se que o catalisador com maior teor de ferro proporcionou uma maior conversão de CO, tendo sido a distribuição de produtos deslocada para as frações mais leves. Comparando os catalisadores de ferro suportados na zeólita KL e na MCM-41 pode-se concluir que as conversões são da mesma ordem de grandeza. Foi observado que o ferro foi mais ativo que o cobalto em termos de conversão do CO, sendo que o cobalto promoveu a formação de uma maior quantidade de produtos na faixa de diesel, assim como uma menor quantidade de leves.
The Fischer- Tropsch synthesis converts the synthesis gas (H2 + CO), in a complex variety of hydrocarbons, using a catalyst (Co/Al2O3 normally) were introduced to the used supports by the wetness incipient impregnation. The samples were analyzed by several techniques such as: plasma- emission spectrometry (ICP- EAS), N2 physical adsorption by BET method, X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electronic microscopy (TEM), hydrogen chemisorption and Infrared Spectroscopy of adsorbed pyridine. The catalysts were evaluated using a fixed bed reactor in the Fischer-Tropsch synthesis. For the iron samples, with the same metal content and different supports, it was observed that the MCM-41 sample presented the lowest reduction level. Among the iron samples supported in KL zeolite, the 5% Fe/KL sample presented the largest reduction level. It was observed by transmission electronic microscopy that the iron particles diameter measured around 6 nm. For the cobalt samples, it was observed that the reduction temperature of the MCM-41 supported was the highest one. The 5% Co/KL sample presented the largest reduction level. It was observed by TEM that the cobalt particles presented diameters in the range from 8 to 20 nm. It was verified that the catalyst with the largest iron percentage promoved the highest CO conversion. The products distribuition was shifted to light fractions. It was observed similar conversions to iron catalysts supported in the KL zeolite and in the MCM- 41 mesoporous molecular sieve. The iron catalysts were more active than the cobalt ones in the CO conversion, but tha cobalt catalysts promoted a higher content of diesel fraction and lesser light fractions.

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Nowak, Emilia. "Bubbles-catalysts-oil interactions at elevated temperature and pressure in Fischer Tropsch synthesis". Thesis, University of Birmingham, 2013. http://etheses.bham.ac.uk//id/eprint/4677/.

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Driving force for this research is dictated by the fact that resources of crude oil, key source of energy in our Everyday life, are limited. Therefore the extensive work is currently carried out to find alternatives such as fully Synthetic fuels - Fisher Tropsch synthesis (FTS). Though FTS was developed in 1923 until recently it was Nearly forgotten. Recent prices of crude oil make this technology attractive again and new research aimed at Optimisation is necessary. The aim of this work was to investigate the behavior of different catalyst in gas/oil dispersion and the effect on Overall mass transfer rate. Efficiency of the entire synthesis, specifically, what is the effect of steam at those Conditions was investigated, since there is practically no information in open literature. This work shows summary of the similarities and differences of properties of all the investigated catalyst and Evaluation of their performance. It was shown that the interactions and ultimately the effect that particles have On the bubble size made of either polar or non-polar gas depends on the particles lyophobicity.

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Almkhelfe, Haider H. "Scalable carbon nanotube growth and design of efficient catalysts for Fischer-Tropsch synthesis". Diss., Kansas State University, 2017. http://hdl.handle.net/2097/38213.

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Doctor of Philosophy
Department of Chemical Engineering
Placidus B. Amama
The continued depletion of fossil fuels and concomitant increase in greenhouse gases have encouraged worldwide research on alternative processes to produce clean fuel. Fischer-Tropsch synthesis (FTS) is a heterogeneous catalytic reaction that converts syngas (CO and H₂) to liquid hydrocarbons. FTS is a well-established route for producing clean liquid fuels. However, the broad product distribution and limited catalytic activity are restricting the development of FTS. The strong interactions between the active metal catalyst (Fe or Co) and support (Al₂O₃, SiO₂ and TiO₂) during post-synthesis treatments of the catalyst (such as calcination at ~500°C and reduction ~550°C) lead to formation of inactive and unreducible inert material like Fe₂SiO₄, CoAl₂O₄, Co₂SiO₄. The activity of FTS catalyst is negatively impacted by the presence of these inactive compounds. In our study, we demonstrate the use of a modified photo-Fenton process for the preparation of carbon nanotube (CNT)-supported Co and Fe catalysts that are characterized by small and well-dispersed catalyst particles on CNTs that require no further treatments. The process is facile, highly scalable, and involves the use of green catalyst precursors and an oxidant. The reaction kinetic results show high CO conversion (85%), selectivity for liquid hydrocarbons and stability. Further, a gaseous product mixture from FTS (C1-C4) was utilized as an efficient feedstock for the growth of high-quality, well-aligned single-wall carbon nanotube (SWCNT) carpets of millimeter-scale heights on Fe and (sub) millimeter-scale heights on Co catalysts via chemical vapor deposition (CVD). Although SWCNT carpets were grown over a wide temperature range (between 650 and 850°C), growth conducted at optimal temperatures for Co (850°C) and Fe (750°C) yielded predominantly SWCNTs that are straight, clean, and with sidewalls that are largely free of amorphous carbon. Also, low-temperature CVD growth of CNT carpets from Fe and Fe–Cu catalysts using a gaseous product mixture from FTS as a superior carbon feedstock is demonstrated. The efficiency of the growth process is evidenced by the highly dense, vertically aligned CNT structures from both Fe and Fe–Cu catalysts even at temperatures as low as 400°C–a record low growth temperature for CNT carpets obtained via conventional thermal CVD. The use of FTS-GP facilitates low-temperature growth of CNT carpets on traditional (alumina film) and nontraditional substrates (aluminum foil) and has the potential of enhancing CNT quality, catalyst lifetime, and scalability. We demonstrate growth of SWCNT carpets with diameter distributions that are smaller than SWCNTs in conventional carpets using a CVD process that utilizes the product gaseous mixture from Fischer-Tropsch synthesis (FTS-GP). The high-resolution transmission electron microscopic (HR-TEM) and Raman spectroscopic results reveal that the use of a high melting point metal as a catalyst promoter in combination with either Co (1.5 nm ± 0.7) at 850ºC or Fe (1.9 nm ± 0.8) at 750ºC yields smaller-diameter SWCNT arrays with narrow diameter distributions. Scalable synthesis of carbon nanotubes (CNTs), carbon nanofibers (CNFs), and onion like carbon (OLC) in a batch reactor using supercritical fluids as a reaction media is demonstrated. The process utilizes toluene, ethanol, or butanol as a carbon precursor in combination with ferrocene that serves as a catalyst precursor and a secondary carbon source. The use of supercritical fluids for growth does not only provide a route for selective growth of a variety of carbon nanomaterials, but also provides a unique one-step approach that is free of aggressive acid treatment for synthesis of CNT-supported metallic nanoparticle composites for catalysis and energy storage applications.

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Govender, Alisa. "Cobalt core-shell nanoparticles as precursors for cobalt-based Fischer-Tropsch synthesis catalysts". Doctoral thesis, Faculty of Engineering and the Built Environment, 2018. http://hdl.handle.net/11427/30007.

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Core-shell nanoparticles may have an economic advantage over traditional nanoparticles as a catalyst, since the expensive, catalytically active material, which is subsurface, may be replaced with a cheaper counterpart. Furthermore, core-shell nanoparticles may be tailored to have a specific structure and composition at the nanoscale, due to a mixing of electronic properties of each phase and/or geometric effects. In this study, nickel ferrite (NiFe2O4) and zinc ferrite (ZnFe2O4) were chosen as core materials around which a cobalt (II, III) oxide (Co3O4) shell was grown. These ferrites were chosen due to their structural similarity to Co3O4 as this was expected to allow an epitaxial growth of the Co3O4 shell onto the ferrite core. Additionally, the difference in the lattice parameter between each ferrite core and the Co3O4 shell was postulated to introduce a varying degree of strain onto the shell, particularly after reduction when metallic cobalt should be present. Core-shell nanoparticles with either a nickel ferrite (NiFe2O4) core or a zinc ferrite (ZnFe2O4) core and a cobalt (II, III) oxide (Co3O4) shell (NiFe2O4@Co3O4 and ZnFe2O4@Co3O4 respectively) were synthesized, characterized and tested for their performance in the Fischer-Tropsch synthesis. These core-shell systems were compared to each other to evaluate the influence of the core and the applicability of NiFe2O4 or ZnFe2O4 as core nanoparticles in a cobalt-based Fischer-Tropsch catalyst. NiFe2O4@Co3O4 core-shell nanoparticles were also supported on Stöber silica spheres to determine the effect of the support on its properties and performance. The influence of two different reduction conditions, viz. 180°C (1 hour) or 230°C (2 hours), on the structure and Fischer-Tropsch synthesis performance of unsupported and Stöber silica spheres supported NiFe2O4@Co3O4 core-shell nanoparticles was also studied. Prior to the preparation of the core-shell nanoparticles, each ferrite core was prepared using the citrate precursor method. A Fe/M mole % ratio (where M is Ni or Zn) of 2.3 and calcination temperature of 450°C yielded phase pure NiFe2O4 or ZnFe2O4 nanoparticles with an average size of 14 nm. Using nickel ferrite (NiFe2O4) nanoparticles as a core, the growth of cobalt (II, III) oxide (Co3O4) around the core was studied by following a homogeneous precipitation synthesis. It was established that a two-step synthesis route was needed to synthesize the core-shell material with a fairly uniform Co3O4 shell. It was found that for both NiFe2O4@Co3O4 and ZnFe2O4@Co3O4 core-shell nanoparticles, the assynthesized materials had a Co3O4 shell around the ferrite core with an average thickness of 2 nm. NiFe2O4@Co3O4 and ZnFe2O4@Co3O4 core-shell nanoparticles were compared to each other as precursors for Fischer-Tropsch synthesis catalysts. Here, the first report on the nanoscale restructuring during reduction of these core-shell nanoparticles in pure hydrogen at 230°C and 250°C, respectively, was observed. This resulted in the formation of small cobalt islands on the ferrite surface. Catalytic testing of the core-shell materials, NiFe2O4@Co3O4 and ZnFe2O4@Co3O4, after reduction showed a cobalt-time yield of 13.64 µmolCO .gCo -1.s -1 and 4.27 µmolCO .gCo -1.s -1 and a C5+ selectivity of 47 C-% and 68 C-%, respectively. The observed difference in cobalt-time yield and selectivity between NiFe2O4@Co3O4 and ZnFe2O4@Co3O4 core-shell nanoparticles was due to a combination of effects that included the presence of cobalt islands over the surface of the core and the difference in extent of reduction of each core under Fischer-Tropsch synthesis conditions. The core-shell structure in NiFe2O4@Co3O4 core-shell nanoparticles was found to be retained with the use of mild reduction conditions of 180°C (1 hour). Thus, the performance in the Fischer-Tropsch synthesis of a system with a true core-shell structure with a cobalt shell was established. The former has not been reported to date. Owing to the former, strain effects may have contributed to NiFe2O4@Co3O4 core-shell (reduced at 180°C, 1 hour) having a low cobalt-time yield of 8.40 µmolCO .gCo -1.s -1 and a C5+ selectivity of 38 C-% during the Fischer-Tropsch synthesis. It was also shown that NiFe2O4@Co3O4 core-shell nanoparticles reduced at 180 °C (1 hour) had a similar activity to unsupported Co3O4, however, the former had a higher C5+ selectivity. The differences in the performance between NiFe2O4@Co3O4 core-shell (reduced at 180°C, 1 hour) and unsupported Co3O4 may have been due to strain effects. The nanoscale structural and compositional differences induced by each reduction condition applied may have been the cause for the inferior Fischer-Tropsch synthesis performance of these core-shell nanoparticles after reduction at 180°C for 1 hour than 230°C for 2 hours. The effect of a Stöber silica spheres support on the characteristics and Fischer-Tropsch synthesis behavior of NiFe2O4@Co3O4 core-shell nanoparticles was also investigated. Prior to characterization and the Fischer-Tropsch synthesis, NiFe2O4@Co3O4/SiO2 was reduced at either 180°C for 1 hour or 230°C for 2 hours. A higher cobalt-time yield (23.80 µmolCO .gCo -1.s -1) with a lower C5+ selectivity (44 C-%) was obtained with reduction at 230°C (2 hours) than 180°C (1 hour). After reduction at 230°C (2 hours), the influence of the support was clearly seen due to the higher activity obtained with NiFe2O4@Co3O4/SiO2. However, the unsupported and supported NiFe2O4@Co3O4 nanoparticles had similar product selectivities. After reduction at 230°C for 2 hours and exposure to Fischer-Tropsch synthesis conditions, the core-shell structure was retained in NiFe2O4@Co3O4/SiO2 possibly due to reducing the contact between the individual core-shell nanoparticles due to the presence of the support. This would be enhanced by anchoring the core-shell nanoparticles onto the Stöber silica spheres support.

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Chirinos, Maruri Ada Elida. "Influence of preparation techniques on the Fischer-Tropsch performance of supported cobalt catalysts". Doctoral thesis, University of Cape Town, 2003. http://hdl.handle.net/11427/5365.

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Includes bibliographical references.
Cobalt based catalysts are generally used for the FT synthesis due to their high activity and selectivity for linear hydrocarbons, low activity for the water gas shift reaction and lower price compared to noble metals [22]. There can, however, be a large effective loss of active metal due to strong metal-support interaction forming complexes that are not reduced at temperatures below 400°C.

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Kunene, Avela. "AuPt nano-alloys as reduction promoters for Co/TiO₂ Fischer-Tropsch catalysts". Master's thesis, University of Cape Town, 2014. http://hdl.handle.net/11427/13375.

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Includes bibliographical references.
Cobalt-based catalysts for the Fischer-Tropsch synthesis are typically promoted with noble metals to achieve a more facile reduction of Co₃O₄ to the catalytically active metal, Co⁰. Hydrogen spillover is thought to be the dominant mechanism for the functioning of noble metals during the reduction process. Platinum is a well-known reduction promoter and its functioning as a reduction promoter is thought to occur via H₂ - spillover mechanism. This process is switched off during the Fischer-Tropsch synthesis, when platinum is used as a reduction promoter, since platinum has been shown to be catalytically inert under these conditions, due to strong adsorption of CO. Some hydrogen spill-over during the Fischer-Tropsch synthesis might be desired to obtain more stable catalysts (less coking), but this effect has to be balanced against increased methanation activity.

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Erasmus, Willem Johannes. "Preparation of model cobalt catalysts for Fischer-Tropsch synthesis using ultrasound preparation techniques". Master's thesis, University of Cape Town, 2006. http://hdl.handle.net/11427/5335.

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Includes bibliographical references (leaves 84-87).
In order to study the oxidation behaviour of small cobalt crystallites during Fischer-Tropsch synthesis, it is necessary to prepare model catalysts with cobalt crystallites of which the size distributions can be adjusted. Here ultrasonication was used to decomposed a tricarbonyl precursor in n-decane to prepare small cobalt crystallites. The aim of this study was to vary the cobalt crystallite size distribution by adjusting the preparation conditions. Transmission Electron Microscopy (TEM) was used to measure the crystallites and to obtain the crystallite size distributions.

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Hauman, Magdalena Maria. "Fundamental understanding of re-dispersion of cobalt on supported model Fischer-Tropsch catalysts". Master's thesis, University of Cape Town, 2011. http://hdl.handle.net/11427/11096.

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The aim of this study was to investigate how the catalytically active material may redisperse during consecutive oxidation-reduction steps (OROR) for a model supported-cobalt catalyst to give insight into the regeneration process of a spent supported-cobalt FTS catalyst.

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Goho, Danielle Sympathie. "Selective production of nitrogen-containing compounds via a modified Fischer-Tropsch process". Master's thesis, Faculty of Engineering and the Built Environment, 2021. http://hdl.handle.net/11427/33736.

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Research on the co-feeding of ammonia into the Fischer-Tropsch (FTS) process over ironbased catalysts revealed that the presence of ammonia during the FTS leads to the formation of nitrogen-containing compounds (NCCs). Recent studies on the addition of ammonia to the FTS process, now known as the Nitrogen Fischer-Tropsch (NFTS) process, reported that the production of NCCs during the NFTS process is enhanced by the presence of oxygenates. The studies, therefore, suggested that oxygenates are the primary precursors of NCCs. However, due to the gap in knowledge related to the NFTS reactions mechanisms, the validity of this assumption is still unknown. In this thesis, the aim was to investigate the correlation between the presence of oxygenates under the FTS conditions and the formation of NCCs under the NFTS conditions and check the suitability of various iron-based catalysts for the NFTS process. From literature, four ironbased catalysts, known for yielding a high percentage of oxygenates, were identified, synthesised, characterised and then tested under FTS conditions to determine the optimum reaction conditions for oxygenates formation. It was found that high oxygenates selectivity can be achieved at low temperature and high space velocity as at these operating conditions the occurrence of secondary reactions involving oxygenates are limited. Furthermore, the catalysts were tested under NFTS conditions to determine their catalytic performance and their selectivity towards NCCs. During the NFTS process, in addition to the decrease in the CO conversion, a significant drop in the oxygenates and CO2 selectivity followed by the formation of NCCs were observed. These results confirmed a sight activity inhibiting effect of ammonia and pointed out the correlation between the presence of oxygenates and the formation of NCCs under FTS and NFTS processes respectively. At the conditions applied, selectivities of up to 17.9 C% of NCCs (predominantly nitriles) could be obtained. This modified process may therefore be considered as an important variation of the FTS process with greatly enhanced chemicals production potential.

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