Tesi: "Fischer-Tropsch process"

1

Frederick), Potgieter Hennie (Hendrik. "Fischer-Tropsch ionomeric waxes". Thesis, Stellenbosch : Stellenbosch University, 2003. http://hdl.handle.net/10019.1/53427.

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Thesis (PhD)--Stellenbosch University, 2003.
ENGLISH ABSTRACT: This dissertation describes work done on Fischer- Tropsch ionomeric waxes. The waxes are characterized with respect to the method of manufacture, the mechanism of the oxidation process, the saponification, the physical properties, the rheological properties, the morphology and the water absorption of the waxes. Different methods of physical and mechanical analysis are used to prove at which concentration level, for each type of cation tested arid for each type of oxidized and grafted wax prepared, the formation of multiplets and clusters within the Fischer- Tropsch ionomeric waxes takes place. An understanding of multiplet and cluster formation in Fischer- Tropsch ionomeric waxes is essential as these morphological phenomena control the mechanical and physical behaviour of the Fischer- Tropsch ionomeric waxes. The ability to be able to analyse the Fischer- Tropsch ionomeric waxes for multiplet and cluster formation should allow one to predict the physical and mechanical behaviour of the Fischer- Tropsch ionomeric waxes in practical applications.
AFRIKAANSE OPSOMMING: Hierdie skripsie beskryf werk gedoen op Fischer-Tropsch ionomeries wasse. Die wasse is gekarakteriseer ten opsigte van die vervaardigingsmetode, die meganisme van oksidasie, die verseping, hulle fisiese en reologiese eienskappe, hulle morfologie en water absorpsie. Verskillende metodes van fisiese en meganiese analiese is gebruik om te bewys by watter konsentrasie, vir 'n spesifieke katioon en vir 'n spesifieke geoksideerde of entwas, wanneer veelvoud of tros-vorming plaasvind. Die vermoë om te verstaan hoe en wanner veelvoude en trosse in Fischer- Tropsch ionomeries wasse vorm is van kardinale belang, aangesien die fisiese en meganiese eienskappe van die Fischer- Tropsch ionomeries wasse direk beinvloed word deur die vorming van veelvoude en trosse. Die vermoë om Fischer- Tropsch ionemeries wasse te kan analiseer vir veelvoud en tros vorming is voordelig om Fischer- Tropsch ionomeries wasse se meganiese en fisiese eienskappe in praktiese aanwendings te voorspel.

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2

Finch, Karol Paula. "Synthesis, characterisation and reactivity studies of μ(α, ω)-alkanediyl complexes of ruthenium, iron and cobalt". Master's thesis, University of Cape Town, 1988. http://hdl.handle.net/11427/21938.

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The new series of μ(α, ω)-alkanediyl compounds of ruthenium, [CpRu(CO)₂]₂[μ-(CH₂)ₙ], where n=5-10, have been prepared from Na[CpRu(CO)₂] and the corresponding diiodoalkane. These compounds, which are stable crystalline solids at ambient temperature, have been fully characterised by microanalysis, infrared, ¹H and ¹³C NMR spectroscopy, melting point and mass spectrometry. The new heterodinuclear complex [Cp(CO)₂Fe(CH₂)₄Ru(CO)₂Cp] has been synthesised by the reaction of [CpFe(CO)₂(CH₂)₄I] with Na[CpRu(CO)₂] and characterised by all the above mentioned techniques.

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3

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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4

Pienaar, Andrew. "Metal carboxylate complexes relevant to the Fischer-Tropsch synthesis". Thesis, Link to the online version, 2005. http://hdl.handle.net/10019/1158.

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5

Govender, Nilenindran Sundra. "Recycling the tail-gas during the low temperature Fischer-Tropsch process". Master's thesis, University of Cape Town, 2005. http://hdl.handle.net/11427/5328.

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Includes bibliographical references (leaves 98-106).
For the economically viable operation of an iron-based Fischer-Tropsch technology, two options are available: (i) use a diluted feed, such as nitrogenrich synthesis gas, thereby saving on synthesis gas costs [Jess et aI., 1999] or (ii) recycle of the unconverted synthesis gas that leaves the reactor, after condensation of the liquid products (or use a number of reactors in series with intermediate condensation of the products). The tail-gas from the FischerTropsch reactor contains un-reacted synthesis gas, CO2, water vapour and lower hydrocarbons (oletins, paraffins and oxygenates). This stream can in principle be recycled back to the Fischer-Tropsch reactor, and thereby reducing the load on the reformers. However, it is necessary to understand what effects the constituents in the tail gas will have on the Fischer-Tropsch process when this stream is recycled back directly to the Fischer-Tropsch reactors.

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6

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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7

Lee, Yong Joon Chemical Sciences &amp Engineering Faculty of Engineering UNSW. "Synthesis, characterisation, and evaluation of supported cobalt molybdenum nitride for Fischer-Tropsch reaction". Publisher:University of New South Wales. Chemical Sciences & Engineering, 2008. http://handle.unsw.edu.au/1959.4/41487.

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

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8

Steynberg, Andre Peter. "Process intensification for the iron-catalysed slurry-phase Fischer-Tropsch Reactor System". Master's thesis, University of Cape Town, 2014. http://hdl.handle.net/11427/13279.

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Includes bibliographical references.
A set of operating conditions was identified with the potential to enable improved slurryphase reactor productivity for hydrocarbon production using Fischer-Tropsch synthesis. Compared to the most relevant prior art publication, this requires operation at higher gas velocity, higher catalyst concentration and at higher temperature and/or pressure. The closest prior art proposal was published by Van der Laan et al. (1999) and a target was set to improve the reactor productivity by at least 50 %, relative to this reference, while also ensuring stable catalyst performance. Prediction of gas holdup in the reactor is essential to determine the reactor productivity and previous correlations used to predict gas holdup are potentially unreliable for extrapolation to the new proposed conditions. A new approach is adapted, from previous theoretical approaches, to provide a more fundamental and reliable basis for gas holdup prediction. Referred to as the ¡®adapted two-phase theory¡¯ it predicts the gas holdup at any slurry solids concentration using data from a representative solids-free liquid. This approach is shown to provide accurate predictions for paraffinic liquids using data covering a wide range of solids concentrations. Two laboratory reactor experiments were performed, at 260 and 270 ¢ªC, to characterise the selected catalyst performance at conditions relevant to the newly proposed operating regime. An achievable reactor performance was calculated corresponding to the catalyst performance from the experiment at 270 ¢ªC and using the new approach to predict gas holdup. Compared to the proposal by Van der Laan et al. (1999), a reactor with a given diameter is able to produce almost double the amount of product (94 % more with a lower slurry bed height). This is achievable by using higher catalyst concentrations and, most importantly, using a higher operating temperature. The undesirable methane selectivity, at or below 4 %, is still acceptable when operating at 270 ¢ªC. In spite of the higher reactor productivity with increasing temperature, the optimum operating temperature, in the range from 250 to 270 ¢ªC, may depend on the selectivity to the desired hydrocarbon products. The scope for further potential reactor productivity improvement is described. More work is needed to accurately quantify the selected iron catalyst selectivity performance, in the proposed temperature range, but the hydrocarbon selectivity was found to be insensitive to other operating conditions (i.e. pressure and gas composition). It is now possible to better quantify the reactor productivity in the trade-offs which are made with the selectivity performance and the overall plant design configuration which requires recycle of carbon dioxide to the methane reformers to adjust feed gas H2/CO ratio for natural gas applications. The carbon dioxide selectivity for the selected catalyst at the conditions tested was found to be too high for gas-to-liquid (GTL) applications using a natural gas feed.

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9

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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10

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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11

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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12

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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13

Whiting, Gary Ken. "Development of a microreactor system for unsteady-state Fischer- Tropsch synthesis". Diss., Virginia Polytechnic Institute and State University, 1985. http://hdl.handle.net/10919/76086.

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Vibrofluidized microreactor systems have been developed for studies of unsteady-state Fischer-Tropsch synthesis. This development is aimed at preventing carbon deposition on a fused-iron catalyst in a novel reactor called the “heat-tray.” This reactor involves a supernatant gas flowing over a shallow fluidized bed of catalyst particles. Three systems were built: (1) a vibrofluidized-bed microreactor system for obtaining baseline carbon deposition infonnation under industrially important reaction conditions; (2) a sliding-plug vibrofluidized-bed microreactor system for rapid switching of feed gases in the F-T synthesis; and (3) a cold-flow microreactor model for studying the gas mixing characteristics of the sliding-plug vibrofluidized-bed microreactor. The results show that catalyst defluidization occurred under steady-state synthesis conditions below 395°C using a feed gas of H₂/CO ratio of 2:1 or less. Above 395°C, the probability of hydrocarbon chain growth (α) on the fused-iron catalyst was low enough (α < 0.50) to prevent accumulation of high-molecular-weight species that cause defluidization. Carbon deposition was rapid above 395°C when a feed gas of H₂/CO ratio of 2:1 or less was used. Spent catalyst fractions in the form of free-flowing catalyst and "bugdust" were quantitatively analyzed for carbon and iron. Mössbauer spectroscopic analysis of free-flowing catalyst showed mainly Hägg carbide (x-Fe₅C₂) and magnetite (Fe₃O₄) with a smaller fraction present as α-Fe. Scanning electron microscopic analysis of the bugdust revealed a mass of highly porous, fine particles with a high carbon content (18-30 wt%). Cold-flow microreactor model studies show that rapid (on the order of seconds), quantitative switching of feed gases over a vibrofluidized-bed of catalyst could be achieved. Vibrofluidization of the catalyst bed induced little backmixing of feed gas over the investigated flow-rate range of 417 to 1650 actual mm³/s. Further, cold-flow microreactor model studies showed intense solid mixing when a -150+300 µ bed of fused-iron catalyst was vibrofluidized at 24 cycles per second with a peak-to-peak amplitude of 4 mm. The development of this microreactor system has provided an easy way of accurately determining integral fluid-bed kinetics in a laboratory reactor. Further, the unique ability of the microreactor system to rapidly switch feed gases over an intensely-mixed solid has important applications in chemical kinetics and reaction engineering.
Ph. D.

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14

Teoh, Wey Yang Chemical Sciences &amp Engineering Faculty of Engineering UNSW. "Flame spray synthesis of catalyst nanoparticles for photocatalytic mineralisation of organics and Fischer-Tropsch synthesis". Awarded by:University of New South Wales. School of Chemical Sciences and Engineering, 2007. http://handle.unsw.edu.au/1959.4/28259.

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In this thesis, a range of TiO2-based photocatalysts and cobalt-based Fischer-Tropsch (FT) catalysts were developed and synthesised via the one-step Flame Spray Pyrolysis(FSP). The work starts with the demonstration of bare TiO2 nanoparticles synthesis with controlled characteristics such as specific surface areas, crystallite sizes and anatase content. A comparative study was carried out by benchmarking with commercial Degussa P25 TiO2. The FSP TiO2 was shown to be more efficient in mineralising pollutants requiring direct charge transfer such as the saccharides, while P25 was better for mineralising alcoholic and aromatic compounds. Both catalysts were equally as active in mineralising carboxylic acids. Upon identifying the optimal synthesis of bare TiO2, an in situ co-precipitation of highly dispersed Pt on TiO2 was carried out in the flame. Deposition of Pt resulted in enhanced photocatalytic performance as a result of efficient charge trappings. It is highlighted here the inter-relationship between Pt oxidation states and the TiO2photocatalysis of carboxylic acid, alcohol and aromatic compounds. Depending on the mineralisation path adopted by the model organic compounds, they were shown to have direct influence on the Pt oxidation states. These oxidation states in turn affect the mineralisation rates of the organic compounds. Substitutional-doping of TiO2 with Fe(III) with tunable bandgap was also possible by FSP synthesis. The high temperature synthesis coupled with rapid quenching resulted in 5 times higher solubility limit (Fe/Ti = 0.05) than that previously reported in the literature. Under visible light irradiation, FSP-made Fe-TiO2 improved the photocatalytic mineralisation of oxalic acid by more than 6 times, with respect to P25 and FSP TiO2. Furthermore, the photocatalyst was reusable over a number of repetitions with minimal leaching or loss in activity. The last part of the work concerns the development of bare and Ru-doped Co-ZrO2 catalysts, where cobalt was finely dispersed within the zirconia matrix. Doping of Ru enhanced significantly the reducibility of cobalt, reducing even the embedded cobalt beneath the zirconia surface. It also increased the extent of CO-chemisorption and as such, enhanced the FT activity. This is the first time, catalysts of such type is synthesised and tested for FT reaction.

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15

Fraser, Ian. "The feasibility of high synthesis gas conversion over ruthenium promoted iron-based Fischer Tropsch catalyst". Thesis, Cape Peninsula University of Technology, 2017. http://hdl.handle.net/20.500.11838/2588.

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Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2017.
One of the very promising synthetic fuel production strategies is the Fischer-Tropsch process, founded on the Fischer-Tropsch Synthesis, which owes its discovery to the namesake researchers Franz Fischer and Hans Tropsch. The Fischer-Tropsch Synthesis (FTS) converts via complex polymerisation reaction a mixture of CO and H2 over transition metal catalysts to a complex mixture of hydrocarbons and oxygen containing compounds with water as major by-product. The mixture of CO and H2 (termed syngas) may be obtained by partial oxidation of carbon containing base feedstocks such as coal, biomass or natural gas via gasification or reforming. The Fischer-Tropsch (FT) process thus presents the opportunity to convert carbon containing feedstocks to liquid fuels, chemicals or hydrocarbon waxes, which makes, for instance, the monetisation of stranded gas or associated gas a possibility. The FT-process is typically carried out in two modes of operation: low temperature Fischer-Tropsch (LTFT) and high temperature Fischer-Tropsch (HTFT). LTFT is normally operated at temperatures of 200 – 250 °C and pressures of 10 – 45 bar to target production of high molecular weight hydrocarbons, while HTFT is operated at 300 – 350 °C and 25 bar to target gasoline production. The catalytically active metals currently used commercially are iron and cobalt, since product selectivity over nickel is almost exclusively to methane and ruthenium is highly expensive in addition to requiring very high pressures to perform optimally. Fe is much cheaper, but tends to deactivate more rapidly than Co due to oxidation in the presence of high H2O partial pressures. One of the major drawbacks to using Fe as FT catalyst is the requirement of lower per pass conversion which necessitates tail gas recycle to extend catalyst life and attain acceptable overall conversions. A more active or similarly active but more stable Fe-catalyst would thus be advantageous. For this reason promotion of a self-prepared typical LTFT Fe-catalyst with Ru was investigated. A precipitated K-promoted Fe-catalyst was prepared by combination of co-precipitation and incipient wetness impregnation and a ruthenium containing catalyst prepared from this by impregnation with Ru3(CO)12. The catalysts, which had a target composition of 100 Fe/30 Al2O3/5 K and 100 Fe/30 Al2O3/5 K/3 Ru, were characterised using XRD, SEMEDX, ICP-OES, TPR and BET N2-physisorption, before testing at LTFT conditions of 250 °C and 20 bar in a continuously stirred slurry phase reactor.

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Van, der Westhuizen Katriena Elizabet. "Comprehensive multidimensional gas chromatography for the analysis of Fischer-Tropsch products". Thesis, Stellenbosch : Stellenbosch University, 2011. http://hdl.handle.net/10019.1/18006.

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Thesis (PhD)--University of Stellenbosch, 2011.
ENGLISH ABSTRACT: The analysis of Fischer–Tropsch–derived (FT–derived) synthetic crude and derived products is very challenging because of the highly complex nature of these products. In this study, the use of comprehensive multidimensional gas chromatography (GCxGC) with time-of-flight mass spectrometry (TOF-MS) and flame ionisation detection (FID) was investigated for the analysis of these products and the technique was found to be invaluable for the analysis of these complex mixtures. The compositions of FT synthetic crude, produced at low temperature (LT–FT) and high temperature (HT–FT) processes were compared and the effect that changes in FT reaction temperature has on product formation was investigated. Results for conventional onedimensional GC (1D-GC) and GCxGC were compared. It was found that conventional 1D–GC does not have sufficient peak capacity to separate the thousands of compounds in the HT FT products. GCxGC provides a huge peak capacity of tens-of-thousands to separate highly complex mixtures. Structured chromatograms, where groups of compounds with similar properties are grouped together, aid in peak identification. Moreover, sensitivity at low microgram per milliliter levels is obtained. These attributes enabled accurate analysis of various complex feed and product streams in the FT refinery, and also various final fuel products. The use of GCxGC alone was demonstrated, and also combined with high performance liquid chromatography (HPLC), supercritical fluid chromatography (SFC) and nuclear magnetic resonance (NMR) when even more separation power was needed. HPLC–GCxGC enabled the separation of alkene and cyclic alkane compound classes in oligomerisation products. These compound classes have similar mass spectra, elute in adjacent regions and co–elute even to some extent on the GCxGC contour plot, making differentiation difficult. SFC is a good replacement for HPLC for these applications because it does not use solvents as mobile phases. CO2 is easily evaporated after the separation and does not interfere with the GCxGC separation of the analytes. SFC is also a very good technique to separate the compound classes of alkanes, alkenes, aromatics and oxygenates, and is therefore highly complementary to GCxGC. The combination of GCxGC with NMR data was also found to be very valuable for the identification of branched alkane isomers in LT–FT diesels. GCxGC provides excellent separation of individual compounds but the identification of isomers (except for mono–methyl branching) is difficult because the mass spectra of most of these isomers are similar and not all compounds are in the mass spectral libraries. NMR, on the other hand, is able to distinguish between the individual types of branched isomers but has limited separation power for the complex mixtures. By combining the two techniques, the best of both was obtained. The study found GCxGC to be invaluable for the analysis of the highly complex FT–derived products, while its combination with other techniques such as HPLC, SFC and NMR provided even more separation power.
AFRIKAANSE OPSOMMING: Die hoogs komplekse samestelling van sintetiese ru–olie en afgeleide produkte, afkomstig van Fischer–Tropsch (FT) sintese, bied groot uitdagings aan die analis. Die studie het die gebruik van GCxGC met ’n TOF-MS en FID bestudeer vir die analise van FT produkte en het bevind dat die tegniek van onskatbare waarde is vir die analise van die hoogs komplekse mengsels. Die samestellings van produkte van lae- en hoë-temperatuur FT prossesse is vergelyk en die effek van ’n verhoging in die reaksie–temperatuur op die produk samestelling is ondersoek. Resultate vir 1D–GC and GCxGC is vergelyk en dit was duidelik dat 1D-GC nie naastenby voldoende piekkapasiteit het om al die komponente van die produkte wat tydens die hoëtemperatuur prosses gevorm word, te kan skei nie. Die GCxGC se piekkapasiteit daarteenoor is in die orde van tienduisende wat die skeiding van hoogs komplekse mensels moontlik maak terwyl die tegniek hoogs gestruktureerde kontoerplotte verskaf wat help met identfikasie van komponente. Die tegniek is verder ook baie sensitief en kan komponente op lae μg/mL vlakke waarneem. Hierdie eienskappe het akkurate analise van verskeie FT produkstrome moontlik gemaak. Die kombinasie van GCxGC met HPLC, SFC en KMR het selfs meer skeidingskrag verskaf waar nodig. HPLC–GCxGC het die skeiding van alkene en sikliese alkane moontlik gemaak. Hierdie komponent klasse se massaspektra is feitlik dieselfde en terselfdertyd elueer die twee groepe reg langs mekaar, en oorvleuel soms selfs tot ’n mate, op die GCxGC kontoerplot, sodat dit moeilik is om daartussen te onderskei. SFC is ’n goeie alternatief vir HPLC in meeste toepassings aangesien die tegniek net CO2 gebruik, wat maklik verdamp by kamertemperatuur en nie oplosmiddels gebruik wat se pieke steur met die van die laekookpunt komponente op die GCxGC kontoerplot nie. Skeidings van die komponentgroepe alkane, alkene, aromate en oksigenate is moontlik met SFC en daarom komplimenteer dit die GCxGC skeiding goed aan. Die kombinasie van GCxGC met kern–magnetiese resonansie (KMR) is van waarde gevind om die verskillende tipes vertakkings in ’n lae-temperatuur FT diesel te identifiseer. GCxGC verskaf uitstekende skeiding van individuele komponente maar die identifikasie van die verskilende isomere, behalwe vir die mono-metiel vertakkings, is moeilik aangesien die massaspektra van baie van die komponente soortgelyk is en die komponente nie in die massa spektrum–biblioteke voorkom nie. KMR, aan die ander kant, kan tussen die individuele vertakkings onderskei maar het beperkte skeidingskrag vir komplekse mensels. Deur die twee tegnieke te kombineer is die beste van albei tegnieke bekom. Die studie het bevind dat GCxGC van onskatbare waarde is vir die analise van die komplekse sintetiese FT produkte terwyl die kombinasie met ander tegnieke soos HPLC, SFC and KMR selfs meer skeidingskrag verskaf.

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Elbashir, Nimir O. M. Roberts Christopher B. "Utilization of supercritical fluids in the Fischer-Tropsch synthesis over cobalt-based catalytic systems". Auburn, Ala., 2004. http://repo.lib.auburn.edu/EtdRoot/2004/FALL/Chemical_Engineering/Dissertation/ELBASHIR_NIMIR_25.pdf.

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18

Davies, Andrew James. "Spectroscopic studies of the Fischer-Tropsch process and gas sorption in metal organic frameworks". Thesis, University of Nottingham, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.663251.

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An introduction to reaction intermediates and the techniques used to identify them in this Thesis is outlined. Additionally the Fischer-Tropsch reaction is also described. This reaction is the subject of the work presented in Chapters 2 to 4. Chapter 2 The development of a gas pulse initiated time-resolved lA rig is summarised in this Chapter. The effect of various experimental conditions on the duration of the pulse of gas within the IR cell was explored with the use of a KBr sample. Additionally, a repeat of two relevant studies from the literature was performed in order to validate the results obtained on this new rig. Chapter 3 This Chapter focuses on the Fischer-Tropsch reaction over Co/Ab03. A combination of both rapid-scan FTIA and point-by-point quantum cascade laser spectroscopy was used to elucidate the intermediates involved in the reaction. Transient lA bands in the organic carbonyl region were observed and tentatively assigned to the formation of formyl units on the Co surface, based upon the lA spectra of organometallic analogues. Additionally, 13CO pulsing, as well as studies into the effect of H2 on these bands, were performed in order to further support this identification. Kinetic traces were obtained at variable temperatures in order to obtain the activation energy parameters, which were then compared to the calculated barriers for possible intermediates reported in the literature. The reproducibility of the transients with successive pulses of CO was also probed. Due to the limited IR window, product formation was not observed and, therefore, these intermediates have yet to be definitively linked to the Fischer-Tropsch Reaction. This Chapter also investigates the effect of CO pulsing over two reduced Fe catalysts. Chapter 4 Investigations into the reaction of CO over Fe particles supported in a matrix at low temperature are reported in this Chapter. Metallic Fe nanoparticles embedded in a silica disc were cooled to 100 K under inert conditions and then exposed to CO gas. Rapid formation of carbonyls was observed. Despite being stable at 100 K, warming by a few degrees caused a rapid, partial dissociation of the carbonyl species. Further warming resulted in further dissociation. Chapter 5 This Chapter reports infrared investigations into the gas uptake of Metal Organic Frameworks (MOFs). Unusual behaviour in the uptake of CO2 by a bifunctional MOF, Co(HL de), which exhibited a two-step uptake isotherm, was probed with FTIR. This was originally proposed to be due to two distinct forms of CO2, however IR spectra indicated that a single species of adsorbed CO2 was present within the pores of the MOF before and after the step. Additionally, S02 uptake in NOTT-202 and CO2, S02 and N02 in NOTT-300 was also probed.

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19

Botes, Frederick Gideon. "The addition of HZSM-5 to the Fischer-Tropsch process for improved gasoline production". Master's thesis, University of Cape Town, 2002. http://hdl.handle.net/11427/5353.

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Bibliography: leaves 127-129.
The Fischer-Tropsch process has two important disadvantages with regard to the production of gasoline. Firstly, the carbon number distribution of the product spectrum follows the statistical Schulz-Flory function. This means that principally hydrocarbons of all lengths are produced and that the gasoline selectivity is limited to a theoretical maximum value of about 48%.

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20

Yamada, Shinobu Tomas. "Modelagem e simulação de um reator multitubular em leito fixo com cinética Fischer Tropsch e catalisador de cobalto". [s.n.], 2011. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266893.

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Orientador: Reginaldo Guirardello
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
Made available in DSpace on 2018-08-18T13:21:06Z (GMT). No. of bitstreams: 1 Yamada_ShinobuTomas_D.pdf: 3876142 bytes, checksum: 951723c2abec9e70853595542ea18fe3 (MD5) Previous issue date: 2011
Resumo: Esta tese apresenta a cinética e a fluidodinâmica do processo Fischer Tropsch realizado nos softwares científicos Fortran (Formula Translation) e CFX (Fluidodinâmica Computacional) da AEA Technology plc. O presente trabalho é uma simulação computacional de um sistema catalítico, multifásico, multicomponente e não isotérmico com topologia tridimensional, baseado em catalisador de cobalto suportado, recheio de esferas de aço e meio reacional formado por pseudocomponentes, gás combustível - GLP, nafta - gasolina - diesel, ceras de baixo - médio - alto peso molecular e vapor de água, além do gás de síntese (CO + H2) não convertido. As modelagens da cinética de reação e do balanço de massa estão estruturadas na linguagem de programação Fortran com modelos matemáticos da tecnologia Fischer Tropsch e as modelagens dos balanços de energia, momento e turbulência pelo software computacional CFX, com geometria baseada no Reator Arge Sasol em Leito Fixo composto por cinco domínios (recheio - meio reacional - entrada - saída - parede) e um subdomínio (catalisador), configuradas numa malha com mais de cinco milhões de elementos e um milhão de nós. A cinética é o modelo esquematizado por Sarup-Wojciechowski (1989) com a constante cinética definida pela expressão modificada da lei de Arrhenius. A modelagem da fluidodinâmica é tratada pelas equações de Navier Stokes e turbulência através do modelo k-? e "disperse phase zero equation", complementados pela biblioteca de propriedades fisico-químicas Diadem DIPPR, artigos científicos e experimentos em planta piloto realizados na Unidade de Industrialização do Xisto - Petrobras, São Mateus do Sul - (PR)
Abstract: This thesis presents the fluid dynamics and the kinetics of Fischer Tropsch Process in a fixed bed reactor accomplished in the scientific software Fortran (Formula Translation) and CFX (Computational Fluid Dynamics) of AEA Technology plc. The current work is a computational simulation of the catalytic system, multiphase, multicomponent and non isothermal with 3D topology, that is based on the cobalt supported catalyst, column random packing and the reaction mean treated on pseudo components concept, fuel gas - PLG, naphtha - gasoline - diesel oil, low - medium - high molecular weight waxes and water steam, besides non converted syngas (CO + H2). The kinetics reaction modelling and mass balance are structured in Fortran programming language with mathematic models of Fischer Tropsch technology. Also the energy balance, momentum and turbulence phenomena are structured by CFX, with geometry based on the Arge Sasol Fixed Bed Reactor consisted for five domains (packing - reaction media - in- out - wall) and one subdomain (catalyst), configured in a mesh with more than five million of elements and one million of nodes. The kinetic models are schematized by Sarup-Wojciechowski (1989) equation and the kinetic constant defined according to a modified expression of the Arrhenius law. The modelling of the fluid dinamics are considered on the Navier Stokes fundamental equations and turbulence phenomena through k-? and "disperse phase zero equation", complemented by the physical-chemicals library property Diadem DIPPR, scientifc articles and data referred to pilot plant experiments performed in the Unidade de Industrialização do Xisto - Petrobras, located in São Mateus do Sul - (PR)
Doutorado
Desenvolvimento de Processos Químicos
Doutor em Engenharia Química

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21

Mirzaei, Nima. "Modelling the Production of Biofuels via Olefins Oligomerisation". Thesis, KTH, Skolan för kemi, bioteknologi och hälsa (CBH), 2020. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-282822.

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The technical feasibility of gasoline and diesel range hydrocarbons production through oligomerisation of olefins, starting from biomass with the intermediary steps of gasfication, water-gas shift reaction and syngas-to-olefins synthesis was investigated, through mathematical modelling and simulation on Matlab. The model for the gasifier was based on minimisation of Gibbs free energy and its results showed that higher carbon efficiencies could be achieved at lower pressures and steam inlet, and more inlet energy, by pre-heating the gasifying agents. The water-gas shift reactor was used to increase the ratio of hydrogen to carbon monoxide from the gasifier, before entering the syngas-to-olefins process. A 1-D model was employed to determine the concentration, temperature, and pressure profiles in the reactor. High inlet pressure and temperature were shown to be beneficial, by requiring smaller reactors for the desired ratios to be reached. Experimental data from scientific literature was used for empirical modelling of the Fischer-Tropsch reactor. Partial pressure of CO and H2 amounting to 1 bar, high temperature and H2/CO showed better production of the low olefins. A reaction mechanism and accordingly, rate equations were developed and employed in a plug-flow type reactor model, calculating the concentration profile of the olefins up to C20. High pressures were favourable for the production of heavier fractions, while elevated temperatures showed to cause more cracking of heavy hydrocarbons and consequently, less conversion. Based on the results of individual reactors, an integrated process flow diagram was suggested and optimised for maximum production of low olefins to the oligomerisation reactor (C2-4). The optimisation showed overall carbon efficiency of the process to be around 20%. The reason for this was associated with the choice of catalyst in the FTO process, due to its high selectivity to carbon dioxide.
Den tekniska genomförbarheten av bensin- och dieselproduktion genom oligomerisering av olefiner, från biomassa via förgasning, vatten-gasförskiftsreaktion och syngas-till-olefiner syntes undersöktes genom matematisk modellering och simulering på Matlab. Förgasningsmodellen baserades sig på Gibbs energi minimisering. Ju mindre förgasningstryck desto högre uppnås koleffektivitet. Vatten-gasskift reaktorn användas för att anpassa väte/kolmonoxid förhållande från förgasningsreaktorn till syngas till olefiner rektorn. En 1-D modell utvecklades och beräknade reaktorns koncentrationer, temperatur och tryckprofiler. Högre inlopps tryck och temperaturer leder till mindre reaktorer. Experimentella data från vetenskaplig litteratur användes för att modellara Fischer-Tropsch reaktorn (syngas till olefiner). Partialt tryck av CO och H2 lika med 1 bar, hög temperatur och H2 / CO visade högre produktion av lätta olefiner. En reaktionsmekanism och följaktligen hastighetsekvationer utvecklades för oligomerisering och användades i en pluggflödesreaktor. Modellen beräknade koncentrationer profiler av olefiiner upp till C20.Högre tryck producerar tyngre fraktioner (diesel) medan högra temperaturer främjar krakning. Baserat på resultaten från enskilda reaktorer föreslogs ett integrerat processflödesdiagram och optimerades för maximal produktion av låga olefiner till oligomeriseringsreaktorn (C2-4). Optimeringen visade att den totala koleffektiviteten i processen var cirka 20%. Anledningen till detta var förknippat med valet av katalysator i FTO-processen på grund av dess höga selektivitet för koldioxid.

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22

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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23

Amod, Muhammad Ali. "Carbidization and size effects of unsupported nanosized iron in the low temperature Fischer-Tropsch process". Master's thesis, University of Cape Town, 2012. http://hdl.handle.net/11427/10048.

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Includes abstract.
Includes bibliographical references.
In the process of developing the most efficient production of fuels from coal or natural gas, there have been major advances in the development of the catalysts used. Previous work at the Centre for Catalysis Research, at the University of Cape Town, has shown great potential and provided a much deeper under- standing of the workings of the Fischer-Tropsch catalyst. The research has found that the catalyst crystallite size plays a crucial part in the product selectivity and requires strict control in order to obtain a certain desired product spectrum. The aim of this project is to provide insight on the behavior of various iron oxide crystallite sizes when placed in a CO concentrated environment during catalyst pretreatment. It will also clarify whether the sizes of the nano-crystallites will increase or decrease when the different phases form and which size carbides faster.

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Guillou, Loïc. "SYNTHESE DE FISCHER-TROPSCH EN REACTEURS STRUCTURES A CATALYSE SUPPORTEE EN PAROI". Phd thesis, Ecole Centrale de Lille, 2005. http://tel.archives-ouvertes.fr/tel-00141507.

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La cinétique et l'exothermicité de la synthèse de Fischer-Tropsch en font un réaction délicate à mener. L'utilisation de réacteurs miniaturisés, qui permettent un meilleur contrôle thermique et utilisent des modes de mise en contact des réactifs et du catalyseur essentiellement contrôlés par la diffusion, pourrait apparaître comme un moyen d'améliorer la maîtrise des conditions de synthèse. Le but de ce travail est de proposer des outils permettant l'application et l'étude de la dite synthèse dans des réacteurs de 200μL de volume.
Des réacteurs assemblés à partir de feuillets structurés ont été réalisés. Un méthode de greffage de catalyseur Co/SiO2 sur un inox préalablement traité a été proposée. Le rôle du prétraitement est de permettre l'adhésion du revêtement catalytique sur le substrat. La méthode de greffage par sol-gel assisté par aérosol a permis d'obtenir des films catalytiques d'épaisseur contrôlée.
Les revêtements ont été testés en synthèse de Fischer-Tropsch sous conditions de réactions variables et dans deux réacteurs différents. L'examen des performances expérimentales a permis l'établissement de la vitesse de consommation de CO, modélisée pour les deux environnement fluidiques pour une gamme de conversion de 10 à 30 %. La comparaison avec des systèmes catalytiques similaires souligne le potentiel supérieur des réacteurs structurés miniatures en terme d'accroissement de la productivité principalement.

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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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Menzli, Slim. "WATER FOOTPRINT OF AVIATION FUEL SYNTHESIS BY THE FISCHER TROPSCH PROCESS USING SUGAR CANE WASTE & LANDFILL GAS AS FEEDSTOCKS". Master's thesis, University of Central Florida, 2008. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4018.

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The recent spikes in oil prices have spurred an already bullish demand on biofuels as a source of alternative energy. However, the unprecedented price records set simultaneously by staple food have raised high concerns about potential impacts of biofuels on the global agricultural landscape as fuel and food markets are being inextricably coupled. The revival of interest in the Fischer-Tropsch (FT) process comes into full force since it offers a promising way to produce carbon-neutral liquid fuels which are readily usable with today's existing infrastructure. The FT synthesis offers the possibility of using crop waste as feedstock instead of the crop itself thus avoiding the risk of further straining water and land resources while helping to alleviate the national energy bill and to achieve independence from foreign oil. As the airline industry is the hardest-hit sector with fuel jumping ahead of labor as the primary cost item, this thesis investigates the prospects of the FT process to transform sugar cane waste (namely bagasse, tops and green leaves) and landfill gas in order to produce kerosene (C12H26) as jet fuel for civil aviation. Established chemical correlations and thermodynamics of chemical reactions are used to assess the water footprint inherent to kerosene production using the above feedstocks at optimal conditions of temperature, pressure, catalyst and reactor type. It has been estimated that 9 to 19 gallons of water are needed for every gallon of kerosene produced. In addition, for the case of sugar cane, less land area per unit energy is required compared to ethanol production since all non-food waste of the plant can be used to produce FT fuel as opposed to ethanol which would utilize only the sugar (food) portion of the plant. This translates into a much lower water footprint for irrigation and consequently a lower water footprint overall.
M.S.M.E.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Mechanical Engineering MSME

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27

Bundhoo, Adam. "Contribution à l'étude mécanistique de la synthèse Fischer-Tropsch: préparation et caractérisation de catalyseurs de cobalt et de nickel". Doctoral thesis, Universite Libre de Bruxelles, 2010. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/210084.

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Ce travail de doctorat s’inscrit dans le cadre de la recherche fondamentale inhérente à la réaction catalytique d’hydrogénation du CO, qui permet de produire du pétrole de synthèse à partir des autres ressources fossiles disponibles à l’état naturel (gaz naturel et charbon).

Les objectifs de ce travail s’articulent autour de deux méthodes originales, respectivement de préparation et de caractérisation des catalyseurs. La première permet la formation in situ de catalyseurs par voie oxalique, alors que la seconde est une méthode de cinétique transitoire chimique appliquée à la réaction CO + H2.

Dans un premier temps, la préparation de catalyseurs « modèles » de cobalt et de nickel a été réalisée en faisant intervenir un oxalate comme précurseur à la formation in situ du catalyseur. L’étude de cette méthode de préparation par « voie oxalique » nous a tout d’abord permis de discuter du mécanisme de formation de l’oxalate, que nous envisageons comme une polymérisation faisant intervenir des ligands oxalate tétradentates établissant des ponts entre les atomes métalliques.

La décomposition thermique de l’oxalate de cobalt a été étudiée dans un second temps. Nous nous somme penchés en particulier sur l’influence de l’atmosphère de la décomposition sur la nature du catalyseur obtenu in fine. Utiliser l’hydrogène comme gaz réducteur permet d’obtenir des catalyseurs purement métalliques développant une surface spécifique intéressante.

Ces catalyseurs ont été utilisés pour les études cinétiques transitoires chimiques de la réaction CO + H2. Les phénomènes transitoires observés ont permis de corréler les hypothèses formulées pour l’élaboration d’un mécanisme original initialement proposé par A. Frennet. En particulier, la dépendance des vitesses réactionnelles aux pressions partielles de CO et d’hydrogène permet d’envisager un mécanisme d’allongement de chaîne basé sur la réactivité d’un intermédiaire réactionnel avec les réactifs en phase gazeuse. Au vu des recouvrements de surface sous conditions réactionnelles ainsi que des phénomènes transitoires observés, cet intermédiaire est constitué de plusieurs atomes (carbone, oxygène et hydrogène), et est à l’origine de la formation des produits de la réaction (CH4 et alcanes à plus longues chaînes), dont la désorption en phase gazeuse suit un processus en deux étapes lors duquel l’influence de l’hydrogène est primordiale.

Doctorat en Sciences
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28

McMillian, Michael H. "Combustion analysis and particulate mutagenicity characterization for a single-cylinder diesel engine fueled by Fischer-Tropsch derived liquids". Morgantown, W. Va. : [West Virginia University Libraries], 2002. http://etd.wvu.edu/templates/showETD.cfm?recnum=2303.

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Thesis (Ph. D.)--West Virginia University, 2002.
Title from document title page. Document formatted into pages; contains xvi, 148 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 162-183).

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29

Cardoso, Marco Tsuyama. "Da iluminação das cidades no século XIX às biorrefinarias modernas: história técnica e econômica da gaseificação". Universidade de São Paulo, 2014. http://www.teses.usp.br/teses/disponiveis/86/86131/tde-11032014-171935/.

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Este trabalho tem como objetivo traçar um panorama geral da tecnologia de gaseificação ao longo da história. Inicialmente concebida para obter gás do carvão mineral e possibilitar uma iluminação pública mais eficiente, a gaseificação passou por várias fases. Na virada do século XIX para o XX, quando o town gas perdeu a iluminação pública para a eletricidade, a produção de gás passou a se voltar para aquecimento e cocção. Se novas possibilidades foram criadas a partir da descoberta da síntese de Fischer-Tropsch (que possibilitava a transformação do gás de síntese em líquidos que poderiam substituir combustíveis e matérias-primas para toda a cadeia petroquímica), a resolução dos problemas de logística do gás natural reduziu a importância do gás do carvão mineral também para o aquecimento e cocção. Crises de abastecimento de petróleo, o principal combustível do século XX, motivaram novas iniciativas e novas formas de utilização da gaseificação como, por exemplo, os gasogênios, que gaseificavam biomassa e carvão para movimentar veículos automotores especialmente durante a Segunda Grande Guerra. Já nos períodos de abundância de petróleo a tecnologia acabava por ser abandonada, uma vez que este era muito mais eficiente e conveniente. Na passagem do século XX para o século XXI, entretanto, as preocupações com as mudanças climáticas colocaram em cheque a contínua utilização de combustíveis fósseis entre os quais o petróleo. Nesse contexto abriu-se uma nova perspectiva para a gaseificação de biomassa, uma vez que esta, combinada com as possibilidades criadas pela síntese de Fischer-Tropsch, possibilitou a criação do conceito de biorrefinarias e de toda uma cadeia química a partir de matérias-primas não apenas renováveis, mas que também são residuais e não alimentares. Embora ainda haja desafios técnicos e, principalmente, econômicos a serem alcançados, outros desafios deste século além da questão climática -, os resíduos sólidos urbanos podem constituir-se em uma importante fonte de insumos para o processo de gaseificação.
This dissertation aims to deliver a systematic approach of the history of gasification process. Initially conceived to obtain coal gas to viabilize more efficient lighting for major cities, the gasification process has passed through several phases. During the Nineteenth Century, the town gas (the gas obtained from coal) has revolutionized night life in modern cities. At the turn of the Nineteenth Century, town gas lost public lighting to electricity, and gas from coal had to migrate to heating and cooking. New possibilities were created with the Fischer-Tropsch synthesis in the twenties. This process enabled the transformation of Syngas a product of the gasification process into any kind of hydrocarbon molecule. So, it could have been a useful substitute to oil, mainly during the oil supply crisis. The Twentieth Century was characterized by intense oil utilization in transport, mechanical forces, electricity generation and also creating products like plastic and asphalt. Gasification was seen as a very good alternative supply of raw material for these products, but in fact, the several oil supply crisis of the Twentieth Century were too short for make the gasification feasible. At the end of twentieth century another issue arose to boost gasification initiatives: climate change. Due the greenhouse effect and concerns about its consequences, researchers and companies started projects of biomass gasification to replace fossil fuels - which includes oil. So far, all these initiatives havent shown up as feasible in commercial production, but the opportunity to create a fossil oil substitute from non food raw materials still involves a lot of effort.

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Bezerra, Marcio Barbalho Dantas. "Implementa??o de um modelo computacional para estudo do processo Fischer-Tropsch em reator de leito de lama". Universidade Federal do Rio Grande do Norte, 2010. http://repositorio.ufrn.br:8080/jspui/handle/123456789/15798.

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Made available in DSpace on 2014-12-17T15:01:24Z (GMT). No. of bitstreams: 1 MarcioBDB_DISSERT.pdf: 1427541 bytes, checksum: 4ea4ab1aa3dd7faa960c62967facffc8 (MD5) Previous issue date: 2010-09-30
Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico
This work aims at the implementation and adaptation of a computational model for the study of the Fischer-Tropsch reaction in a slurry bed reactor from synthesis gas (CO+H2) for the selective production of hydrocarbons (CnHm), with emphasis on evaluation of the influence of operating conditions on the distribution of products formed during the reaction.The present model takes into account effects of rigorous phase equilibrium in a reactive flash drum, a detailed kinetic model able of predicting the formation of each chemical species of the reaction system, as well as control loops of the process variables for pressure and level of slurry phase. As a result, a system of Differential Algebraic Equations was solved using the computational code DASSL (Petzold, 1982). The consistent initialization for the problem was based on phase equilibrium formed by the existing components in the reactor. In addition, the index of the system was reduced to 1 by the introduction of control laws that govern the output of the reactor products. The results were compared qualitatively with experimental data collected in the Fischer-Tropsch Synthesis plant installed at Laborat?rio de Processamento de G?s - CTG?S-ER-Natal/RN
O presente trabalho tem como objetivo a implementa??o e adapta??o de um modelo computacional de equil?brio de fases visando o estudo do processo Fischer- Tropsch em reator leito de lama a partir de g?s de s?ntese (CO + H2) para a produ??o seletiva de hidrocarbonetos (CnHm), com ?nfase na avalia??o da influ?ncia das condi??es operacionais sobre a distribui??o dos produtos formados durante a rea??o. O modelo em quest?o leva em conta efeitos do equil?brio de fases de modo rigoroso num tambor flash reativo, uma cin?tica detalhada que prev? a forma??o de cada componente do sistema reacional, bem como malhas de controle do processo para as vari?veis press?o e n?vel da fase lama. O sistema de equa??es obtido ? do tipo Alg?brico Diferencial, e foi resolvido utilizando-se o c?digo computacional DASSL (Petzold, 1982). A inicializa??o consistente do sistema de equa??es foi feita com base na condi??o de equil?brio de fases inicial formado pelos componentes j? existentes no reator, sendo o ?ndice do sistema reduzido a 1 pela introdu??o das leis de controle que regem a sa?da de produtos do reator. Os resultados obtidos foram comparados qualitativamente com os dados experimentais coletados na planta de s?ntese de Fischer- Tropsch instalada no Laborat?rio de Processamento de G?s do CTG?S-ER em Natal/RN

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Tucker, Chelsea Lyn. "Waste to fuel: designing a cobalt based catalyst and process for once-through Fischer-Tropsch synthesis operated at high conversion". Doctoral thesis, Faculty of Engineering and the Built Environment, 2021. http://hdl.handle.net/11427/33059.

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The production of fuels from waste on a small-scale decentralized level may enhance the liquid fuel security of Sub-Saharan Africa. The Fischer-Tropsch process can be used to convert waste into drop-in fuels. However, operating at small scale in remote locations requires a plant design with lower capital requirements, a greater level of simplicity and utility self-sufficiency. A plant design using an air-fed biogas reformer (without an air separation unit) and a single pass Fischer-Tropsch configuration is proposed. A fundamental requirement of this particular design is that it needs to operate at a higher FischerTropsch conversion than typically seen in industry (55 – 65%). High conversion conditions result in a high partial pressure of H2O and low partial pressures of CO and H2 within the Fischer-Tropsch reactor. These conditions have been reported to negatively affect the activity, selectivity and stability of cobalt-based catalysts. To date, no study has investigated the cause of this phenomenon, nor has a catalyst been developed specifically to operate under high conversion conditions. The objective of this study is to investigate the mechanisms behind these phenomena and provide catalyst design improvements that facilitate operation at high conversion conditions. Furthermore, a detailed design of the proposed once-through Fischer-Tropsch biogas-to-fuel plant will be evaluated using data from the catalytic experiments. An investigation into the effect of high conversion on the activity and selectivity of 0.05Pt-22Co/Al2O3 was conducted in a slurry bed reactor at T = 220°C, P = 20 bar, with a feed simulating synthesis gas generated from air-blown reforming (H2:CO:N2= 4:2:6). Space velocity was decreased to increase conversion to between XCO = 40% and XCO = 97%. The rate of CO consumption decreased with increasing conversion. Increasing the CO conversion was found to have negligible effect on CO2 selectivity (an unwanted by-product) up to a CO conversion of 75%, after which a strong increase was observed. This was attributed to the enhanced of water-gas shift activity of Co0 under hydrothermal conditions. The production of CO2 raised the H2/CO ratio within the reactor resulting in a large increase in the CH4 selectivity (an unwanted by-product), a decrease in the chain growth probability and thus a decrease in the C5+ selectivity (fuel product). In order to improve unfavourable selectivity obtained at high conversion in the Fischer-Tropsch synthesis, the effect of adding manganese (Mn) to 0.05Pt-22Co/Al2O3 was explored. The catalyst (0.05Pt22Co/Al2O3) was impregnated with increasing amounts of manganese, resulting in six Mn-Pt-Co/Al2O3 catalysts with Mn:Co mass ratios of 0, 0.04, 0.09, 0.14, 0.23 and 0.47:1. The optimal level of manganese promotion was found at a Mn:Co mass ratio of 0.14:1. At this level of manganese promotion, CO2 and CH4 selectivity was decreased by up to 6 C-% and 12 C-% (XCO = 90%) respectively whilst turn-over frequency was improved by 100%. The maximum in the C5+ yield as a function of CO-conversion was shifted from XCO = 78% to XCO = 91%, thus making operation at high conversion feasible from an activity and selectivity perspective. Operating Pt-Co/Al2O3 at conversion levels higher than XCO = 70% was shown to lead to rapid irreversible deactivation, with a total activity loss of 50% between XCO = 70% and 97%. Using a combination of spent catalyst characterisation via transmission electron microscopy, temperature programmed reduction/hydrogenation as well as an in-situ magnetometer, this irreversible deactivation was attributed to both sintering and cobalt aluminate formation. At very high conversion (XCO > 97%) enhanced reversible deactivation was exhibited due to the oxidation and re-reduction Co0 to Co(II)O. This oxidation/reduction cycle is the result of a thermodynamic conversion limit: at a mean Co0 crystallite size of 6 nm (as obtained with Pt-Co/Al2O3), the maximum achievable conversion (assuming a lognormal distribution of crystallites, σ = 0.5) is XCO = 88%. A log-normal distribution of cobalt crystallites with an average size of 8 nm (and the same variance) is required to obtain a maximum conversion of up to XCO = 98%. In order to limit deactivation due to cobalt aluminate formation at conversions higher than XCO = 70%, zinc aluminate was investigated as a novel support material for a platinum promoted cobalt catalyst. Zinc aluminate thermodynamically limits the formation of cobalt aluminate and facilitates the formation of larger sized cobalt crystallites. The catalyst, 0.04Pt-23Co/ZnAl2O4 exhibited minimal signs of irreversible deactivation at high conversion with a total rate loss of 0.08 mmol /min/g (0.62 to 0.54 mmol /min/g), whilst the rate loss over 0.05Pt-22Co/Al2O3 amounted to 0.47 mmol /min/g (from 0.74 to 0.27 mmol /min/g). The zinc aluminate supported catalyst exhibited equal selectivity towards CO2, CH4 and C5+ as PtCo/Al2O3 and an improved turnover frequency, thus making it a viable replacement support for cobalt under high conversion conditions. A once-through waste-to-fuel process (using biogas from the anaerobic digestion of waste as a raw material) was designed using the experimentally determined selectivity and activity data from the FischerTropsch synthesis. The syngas generation step of this design incorporates a tri-reformer and water-gas shift reactor. Syngas is then fed into the Fischer-Tropsch reactor, which produces largely waxy products at lower conversions (XCO = 60%) and largely naphtha/distillate products at higher conversions (XCO > 80%). The Fischer-Tropsch products were partially refined to distillate (low density diesel) by means of flash tanks and an atmospheric distillation column. At lower conversion levels, a hydrocracker must be used to improve distillate yields. All light hydrocarbons and syngas are fed to a combined cycle power plant, which produced electricity for the plant, thus satisfying the plant's utility self-sufficiency objective. The plant design was evaluated to find an optimal conversion at which to operate, and to gauge the effectiveness of the catalyst design improvements. An optimal conversion of XCO = 80% was found for Mn-Co/Al2O3 (Mn:Co = 0.14) at a production level of 329 bbl/day distillate from a feed of 16 tonnes of municipal solid waste per hour. This represents a 12% increase in production of distillate when compared to Pt-Co/Al2O3 at the same conversion. A shift from an alumina support to a zinc aluminate support will be necessary as the optimal conversion for this process lies above the XCO = 70% deactivation threshold.

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Van, der Westhuizen Rina. "The use of multidimensional GC techniques for the analysis of complex petrochemical products". Thesis, Stellenbosch: University of Stellenbosch, 2005. http://hdl.handle.net/10019.1/4639.

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90 leaves on CD format, preliminary i-ix pages and numbered pages 1-81. Includes bibliography, list of figures in color to pdf format (OCR).
Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005.
ENGLISH ABSTRACT: The composition of petrochemical products obtained from Fischer Tropsch (FT) technologies is of the highest complexity possible and may contain thousands of components. Chemicals produced from FT feedstocks often contain trace level contaminants that can poison catalysts or that affect product performance in down-line processes. Single dimension GC analysis of these mixtures provides incomplete information because of lack of separation power. This study evaluates the separation power of heart-cut GC-GC, comprehensive GCxGC and sequential GC-GC for three selected challenging petrochemical applications. The fundamental theoretical aspects of the techniques are discussed. Oxygenates are removed as far as possible in C10 – C13 alkylation feedstocks, used in the production of linear alkyl benzenes, because the oxygenates may have deactivating effects on some expensive alkylation catalysts. Residual oxygenates may still be present and can consist of hundreds of components. Detection of individual components at ng/g levels is required. Heart-cut GC-GC is used to illustrate the separation and enrichment power for oxygenates in an alkylation feedstock. The stationary phase in the first dimension column was selected to provide separation of the oxygenates from the hydrocarbons in a relatively narrow window. The oxygenate fraction is then enriched by repeated injections and collection on the cryotrap. After sufficient enrichment, the trap is heated and the oxygenates are analysed on the second dimension column. Comprehensive GCxGC and Sequential GC-GC are compared for the separation and analysis of the oxygenated chemical component classes in the alkylation feedstock, before removal of oxygenates. Cyclic alcohols can occur in detergent alcohols produced from FT feedstocks. These cyclics are regarded as impurities because they affect the physical properties of the detergents. The cyclic and noncyclic alcohols in a narrow C12 – C13 detergent alcohol distillation cut have similar boiling points and polarities, and separation of individual components is thus difficult to achieve. Comprehensive GCxGC and sequential GC-GC are evaluated for the separation of the alcohol component classes. The study shows that both approaches provide component class separation but the high resolving power of the second column and the optimal chromatographic operating conditions of sequential GC-GC provide better separation of the individual components. The study illustrates the immense power of the three multidimensional GC techniques namely heart-cut GC-GC, comprehensive GCxGC and sequential GC-GC. The three multidimensional GC techniques each have their own advantages, disadvantages and unique applications and should be used as complementary rather than as competitive analytical tools.
AFRIKAANSE OPSOMMING: Fischer Tropsch (FT) petrochemiese produkte is van baie hoë kompleksiteit en kan uit duisende komponente bestaan. Chemikalië afkomstig van dié voerstrome bevat soms spoorhoeveelhede onsuiwerhede wat deaktiverend op kataliste kan inwerk of wat die werkverrrigting van finale produkte kan beïnvloed. Enkeldimensie GC analises van die komplekse mengsels is meesal onakkuraat as gevolg van geweldige piekoorvleueling. Die studie evalueer die skeidingsvermoë van drie multidimensionele tegnieke, Heart-cut GC-GC, Comprehensive GCxGC en Sequential GC-GC vir geselekteerde petrochemiese toepassings. Die fundamentele teoretiese aspekte van die tegnieke word bespreek en drie analitiese toepassings word beskryf. Oksigenate word so ver moontlik verwyder uit C10 – C13 paraffien-voerstrome, wat gebruik word in die vervaardiging van liniêre alkielbenzene, aangesien dit deaktiverend kan inwerk op alkileringskataliste. Die oorblywende oksigenate kan uit honderde komponente bestaan sodat analise van individuele komponente tot op lae ng/g vlakke nodig is. Heart-cut GC-GC word gebruik om die skeiding en verryking van die oksigenate in die alkileringsvoerstroom te illustreer. Die stationêre fase in die eerste-dimensie kolom is so gekies dat skeiding tussen oksigenate en koolwaterstowwe verkry word. Met herhaalde inspuitings verhoog die oksigenaat-konsentrasie op die cryo val en - na voldoende verryking - word die val verhit en die oksigenate geanaliseer op die tweede dimensie kolom. Die skeiding en analises verkry met Comprehensive GCxGC en Sequential GC-GC word vergelyk vir die chemiese klasse-skeiding van die alkileringsvoer (voor verwydering van oksigenate). Sikliese alkohole kan voorkom in detergent-alkohole vervaardig vanaf FT voerstrome. Dit word as onsuiwerhede beskou aangesien dit die fisiese eienskappe van die finale produkte beïnvloed. Die sikliese en nie-sikliese alkohole se kookpunte en polariteite is baie naby aanmekaar sodat skeiding van individuele komponente moeilik verkry word. Comprehensive GCxGC en Sequential GC-GC word evalueer vir die skeiding van die alkohol. Die studie toon aan dat albei die tegnieke skeiding gee van die chemiese komponent-klasse maar dat die hoë-resolusie tweede-dimensie kolom en die optimisering van die experimentele kondisies van die Sequential GC-GC sisteem beter skeiding van individuele komponente gee. Die uitsonderlike skeidingsvermoë van die drie multidimensionele tegnieke, Heart-cut GC-GC, Comprehensive GCxGC en Sequential GC-GC word geïllustreer in die studie. Elke tegniek het sy eie voordele, nadele en unieke toepassings en die drie tegnieke behoort as komplementêre eerder as kompeterende tegnieke gebruik te word.

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33

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
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34

Critchfield, Brian L. "Statistical Methods For Kinetic Modeling Of Fischer Tropsch Synthesis On A Supported Iron Catalyst". Diss., CLICK HERE for online access, 2006. http://contentdm.lib.byu.edu/ETD/image/etd1670.pdf.

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35

Murdoch, Alexander. "Structural and compositional analysis of cobalt palladium model catalyst surfaces". Thesis, University of St Andrews, 2012. http://hdl.handle.net/10023/3640.

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To date there has been much work carried out in the field of surface science to gain a better understanding of the fundamentals of a wide range of catalytic systems and reactions. The central theme of this thesis relates to cobalt based Fischer-Tropsch synthesis (FTS) with particular focus on the structure, composition and surface chemistry of CoPd bimetallic systems and on the interaction of Co with oxide support materials. In the work described in this thesis MEIS and STM are used to examine the growth of Co on Pd{111} and to characterise the structure of CoPd alloys created by thermal treatment of thin Co films. MEIS investigations indicate that Co grows initially as an fcc overlayer, but beyond a few layers, a stacking fault exists resulting in hcp growth. On annealing between 550 and 700 K, a previously unreported ordered surface alloy is observed giving rise to a p(2 x 1) structure which is concluded to be the surface termination of an ordered CoPd bulk alloy. At higher annealing temperatures, long range Moiré structure is observed by STM which MEIS reveals to correspond to a Pd-rich alloy. MEIS is used to investigate adsorbate induced segregation effects at CoPd surfaces on Pd{111}. The adsorption of O2, CO, H2 and CO/H2 mixtures (syngas) were all examined on a range of bimetallic surfaces. Oxygen adsorption on CoPd alloys strongly segregates cobalt to the surface as a result of the facile oxidation reaction. The behaviour of the components of syngas was more complex with the most noticeable effects being observed on surfaces which were more defect rich. The growth, annealing behaviour and adsorption properties of Co particles on oxide and mixed oxide surfaces are examined using MEIS and TPD.

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Pinilla, Maria Juliana. "Comparative Life Cycle Assessments of Lignocellulosic and Algae Biomass Conversion to Various Energy Products through Different Pathways". Scholar Commons, 2011. http://scholarcommons.usf.edu/etd/3740.

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Bioenergy has the potential to reduce the world's dependence on fossil fuels, and to decrease the CO2 emissions due to fossil combustion. Lignocellulosic and algae biomass have been presented as promising feedstocks for bioenergy production. In this study, a comparative Life Cycle Assessment (LCA) has been developed to evaluate the environmental impacts associated with different energy products via different routes across the whole life of algal and lignocellulosic bioenergy. Results were compared per energy basis, the production of 1 million BTU of energy products. For the development of the comparative algae biomass conversion LCA, algal biomass was converted to liquid biofuels via a thermochemical gasification and Fisher-Tropsch Synthesis (FTS) process; and to electricity and heat via anaerobic digestion and combined heat and power (CHP) process. Overall results from the algae biomass conversion LCA showed that the process that converts algae biomass through anaerobic digestion and CHP process to electricity and heat had the highest overall environmental impact. Results also showed that the impact categories that appear to contribute the most to the overall impacts are ecotoxicity, human health non-cancer, and human health cancer. For the development of the comparative lignocellulosic biomass conversion LCA, lignocellulosic biomass was converted to ethanol and higher alcohols through thermochemical gasification and alcohol synthesis process, to liquid biofuels via thermochemical gasification and FTS process, and to liquid biofuels via a thermochemical gasification and FTS process that uses methane. Overall results from the lignocellulosic biomass conversion LCA showed that the process that converts lignocellulosic biomass into alcohols has the highest overall environmental impact. Results also showed that the impact categories that appear to contribute the most to the overall impacts are ecotoxicity, human health non-cancer, human health cancer, and global warming. This study determined that cultivated algae biomass feedstock has much higher environmental impacts compared with lignocellulosic biomass feedstock from forestation and agriculture byproducts. It was also concluded that thermochemical gasification and FTS process showed higher efficiency when converting biomass to bioenergy. In addition, the five biomass to bioenergy conversion pathways used in the development of this LCA study were compared. Results showed that the pathway with lignocellulosic biomass (feedstock), thermochemical gasification and alcohol synthesis process (conversion process), and ethanol and higher alcohols (energy products) has the largest environmental impact.

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37

Van, Niekerk Bertina Freda. "Functional and structural diversity of the microbial communities associated with the use of Fischer–Tropsch GTL Primary Column Bottoms as process cooling water / van Niekerk B.F". Thesis, North-West University, 2011. http://hdl.handle.net/10394/7284.

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Despite emerging water shortages, most water is only used once, and often with low efficiency. However, with appropriate treatment, water can be re–used to reduce the demand on freshwater sources. The Department of Water Affairs, South Africa, promotes industries to reduce discharges into water resources in order to sustain an overall good water quality of all water systems. All of this ultimately leads to industries striving towards zero effluent discharge. Primary Column Bottoms (PCBs) is a wastewater stream derived from the Fischer–Tropsch Gas to Liquid process and consists mainly of organic acids, but no nitrogen or phosphorous, which by implication excludes possible biodegradation. In the operation of cooling towers in industrial processes, cooling water quality has a direct impact on the cooling performance of the system, where nutrient levels may affect fouling, scaling and corrosion observed in the cooling towers. Fouling, scaling and corrosion affect the operating efficiency of cooling water systems and may necessitate the addition of chemical agents to control these phenomena. This has a financial and labour time impact on the operation of these systems. In this study a mini cooling tower test rig was operated with a synthetic PCB effluent as cooling water and various cycles of concentration, pH and linear flow velocities (LFVs). A constant delta temperature of 10 °C was maintained. Cycles of concentration (COC) evaluated included 2, 4 and 6 cycles of concentration and linear flow velocities evaluated was 0.6 m/s, 0.9 m/s and 1.2 m/s. Fouling, scaling and corrosion rates were determined using corrosion coupons and heat exchanger tubes for mild steel and stainless steel. Besides the evaluation of the various operational parameters for fouling, scaling and corrosion, the possibility for chemical oxygen demand (COD) removal by operating the cooling tower as a bioreactor was also evaluated. To this end nutrient correction was applied to the reactor to allow for a CNP ratio of 100:10:1. With regard to fouling, scaling and corrosion, mild steel was more affected by fouling, scaling and corrosion compared to stainless steel where almost no fouling, scaling and corrosion was observed. Overall increased linear flow velocities resulted in higher fouling and scaling rates, whereas lower linear flow velocities resulted in decreased corrosion rates. In terms of cycles of concentration, increased COC resulted in higher fouling, scaling and corrosion rates. Despite the high nutrient removal levels, the accompanying fouling, scaling and corrosion was still below the particular industry’s guidelines. Besides physical–chemical evaluation of the towers under the various operational conditions, culture–dependent and culture–independent methods were also employed. Concerning culture–dependent approaches the study demonstrated that aerobic and anaerobic organisms are present in both the planktonic and sessile phase of the cooling tower reactors. Heterotrophic aerobes were found to be the most abundant under all the operating conditions. Sulphate reducing bacteria were more abundant in the sessile phase of the cooling towers, and the presence of high sulphate levels in the experiments could be indicative of the sulphate reducing bacteria actively participating in the microbial community. Lower than expected corrosion levels, however, suggest that a combination of the organisms in the biofilm rather than sulphate reducing bacteria alone, contributed to the corrosion rates observed. Culture–independent methods, specifically phospholipid fatty acid analysis supported the results from the culture–dependent methods. Furthermore results demonstrated that linear flow velocity had a greater effect on the community structure than cycles of concentration. Finally molecular methods, specifically denaturing gradient gel electrophoresis, found that increasing cycles of concentration resulted in increased microbial community diversity, while increasing linear flow velocity resulted in decreased microbial community diversity. Regarding COD removal, nutrient correction of the synthetic PCB effluent achieved 89.35 % COD removal at 2 COC and 1.2 m/s LFV, while 80.85 % COD removal was achieved at 4 COC at 1.2 m/s LFV. From these results it was recommended that the operation of the cooling tower should be at 4 COC and 1.2 m/s, which despite slightly lower % COD removal, were characterised by fouling, scaling and corrosion rates well within guidelines.
Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2012.

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38

Mahmoudi, Hamid. "Performance of cobalt-based eggshell catalyst in low-temperature Fischer-Tropsch synthesis process to produce long-chain hydrocarbons from synthesis gas utilizing fixed-bed reactor technology". Thesis, University of Birmingham, 2015. http://etheses.bham.ac.uk//id/eprint/5656/.

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Preliminary studies of the Fischer-Tropsch synthesis (FTS) process were begun in 2010 at the University of Birmingham. A mini-scale F-T plant was designed and built at the School of Mechanical Engineering to study the production of long-chain hydrocarbons over a cobalt-based FTS process. For this purpose, a series of eggshell cobalt catalysts supported with silica powder with a dissimilar porous structure were investigated to examine the effect of support variables on the catalysts’ performance. The prepared catalysts were characterized with nitrogen adsorption/desorption, X-Ray Diffraction (XRD), Temperature-Programmed Reduction (TPR), Scanning-Electron Microscopy (SEM) and Energy-Dispersive X-ray Spectroscopy (EDS) experiments to ensure the qualification of the catalysts for the F-T plant. A highly metal-dispersed catalyst was achieved by controlling three key parameters: (i) cobalt content, (ii) impregnation solution and (iii) meso-porous silica of average pore diameter during catalyst preparation. The catalysts were relatively activated at high temperature because of the formation of small particles. The concentration of the active site was maximized in order to enlarge the hydrogenation activity of the cobalt-based eggshell catalyst to produce middle distillates products. The optimisation study of the F-T process at low-temperature and low/medium pressure was performed to acquire the maximum production of liquid diesel fuel in a single-pass F-T process. The orthogonal arrays’ approach was employed to design a set of experiments. The investigations were successful to maximise the conversion in reactants (up to 98%) and lower the activity of the co-reactions at the same time. The change in reactant consumption and hydrocarbons’ selectivity was monitored over the time on stream and the responsible mechanisms for short-term deactivation within the first reaction cycle were studied, to achieve the optimum reaction conditions in terms of later deactivation of the catalyst.

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39

Crause, Chantelle. "Synthesis and application of carbene complexes with heteroaromatic substituents /". Access to E-Thesis, 2004. http://upetd.up.ac.za/thesis/available/etd-05252005-145146/.

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40

Slabbert, Savia Susanna. "Evaluation of the suitabil[i]ty of Fischer-Tropsch gas-to-liquid (GTL) Primary Column Bottoms as process cooling water : analysis of microbial community dynamics, fouling, scaling and corrosion / Savia Susanna Slabbert". Thesis, North-West University, 2007. http://hdl.handle.net/10394/1309.

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Water in South Africa is becoming limiting due to economic growth, social development and the country's water demand that exceed its water availability. Water conservation in the industry can be accomplished by the reuse of process water instead of direct treatment and discharge. By reusing a process effluent as cooling water in cooling towers, the water requirements of an industry, such as Sasol, will be lower and a zero effluent discharge scenario could be achieved. At Sasol, during the gas-to-liquid (GTL) conversion process, natural gas is converted to diesel and other products. During this process an aqueous effluent stream is produced in the Fischer-Tropsch (F-T) reactors known as Primary Column Bottoms. Primary Column Bottoms can be re-used as cooling water within cooling towers. Although this approach is technically feasible, the re-use of process water in cooling systems is characterised by major problems (fouling, scaling and corrosion) due to the complicated chemistry of the process water and the increased nutrient loads within the system. The aim of this study was to evaluate the suitability of Fischer-Tropsch gas-to-liquid Primary Column Bottoms as process cooling water by analysing the microbial community dynamics, fouling, scaling and corrosion. Due to the corrosive nature of this process effluent, stabilisation of the water was essential. To determine whether efficient stabilisation was attained, an accelerated corrosion test was performed. Influence of the external operating parameters within the cooling tower on the rate of fouling, scaling and corrosion were also determined. Structural and functional diversity of planktonic and sessile communities were studied by making use of conventional microbiological techniques (plate counts, MPN technique) and molecular methods (PLFA, DGGE). The accelerated corrosion test of 28 days conducted on mild steel and stainless steel (316L) corrosion coupons accelerated corrosion by immediately establishing the mature natural environment that causes corrosion. The test solution was stabilised as well as non-stabilised synthetic Primary Column Bottoms, in order to compare the effect of stabilisation. Scaling and corrosion indices were also calculated on stabilised and non-stabilised water to determine the scaling and corrosive tendencies of the water and how this correlates with the actual corrosion results obtained. According to the Langelier Saturation Index (LSI), Rymar Stability Index (RSI) and the Puckorius Scaling Index (PSI) the stabilised water was slightly scale forming with little corrosion and the non-stabilised water being more corrosive than scale forming. Average corrosion rate of the stabilised water was 0.032 m d y and 0.049 m d y for non-stabilised water. Average scaling rate was calculated as 7.269 mg/dm2/d for stabilised water and 5.853 mg/dm2/d for non-stabilised water. It can therefore be concluded that effective stabilisation was achieved since stabilised water was less corrosive than non-stabilised water which was also confirmed through experimental data (corrosion rates from accelerated corrosion test) and corresponded with the corrosive tendencies obtained from the scaling and corrosion indices. A lab-scale cooling tower was operated with stabilised synthetic Primary Column Bottoms as cooling water. Five experiments were conducted under varying flow rates and cycles of concentration. Influence of the external operating parameters (linear flow velocity and cycles of concentration) on fouling, scaling and corrosion rates of mild steel and stainless steel (316L) corrosion coupons and heat exchanger tubes were determined through weight loss measurements. Routine physico-chemical analyses, EDS (energy dispersive spectrometry) microanalysis as well as scaling and corrosion indices of each experiment were also compared, in order to evaluate the influence of cycles of concentration and linear flow velocity. Based on the results obtained, it was evident that the variation in cycles of concentration and linear flow velocity had a significant effect (p0.05) on the fouling, scaling and corrosion rates on the mild steel corrosion coupons and heat exchanger tubes. Experimental runs operated at low flow rates of 0.6mIs and 0.9 d s resulted in relative high fouling, scaling and corrosion rates. Operation at 3 and 4 cycles of concentration had the highest scaling and corrosion rates. The COD within the cooling tower was not removed by the microorganisms within the planktonic and sessile communities and resulted in a build-up of COD in the sump. Thus, the cooling tower cannot be used as a bioreactor to biologically degrade volatile organic acids and hydrocarbons. To evaluate the structural and functional diversity of the bacterial and fungal communities. plate counts, most probable number technique, phospholipid fatty acid (PLFA) analysis as well as denaturing gradient gel electrophoresis (DGGE) was used. According to PLFA profiles the community structure within the planktonic and biofilm samples of the experiments operated at low linear flow velocities were similar. The same percentages of Gram-positive, Gram-negative bacteria and fungi occurred, The community structure composition of the planktonic and sessile phases in the experiments operated at higher linear flow velocities was also similar. PLFA analysis concluded that the highest estimated viable biomass was in experiment 1 which had a low linear flow velocity of 0.6 d s . Shannon-Weaver index analysis of DGGE profiles (general structural diversity) indicated that the planktonic bacterial diversity of experiment I and 2 were the highest. Experiment I and 2 were operated at a linear flow velocity of 0.6 and 0.9 m/s respectively. The biofilm samples that had the highest Shannon-Weaver diversity index were experiment 1 and 5. Both experiment 1 and 5 were operated at a linear flow velocity of 0.6 m/s. Morphological changes between planktonic and sessile communities were monitored through scanning electron microscopy (SEM). SEM results illustrated that the planktonic and sessile microbial populations throughout the five experiments were similar, based on morphology. According to the results obtained from the MPN technique, the experiment operated at the lowest linear flow velocity had the highest numbers of sulphate reducing bacteria and also resulted in the highest corrosion rate. Both experiments that were operated at a low linear flow velocity of 0.6 d s had the highest bacterial numbers and also resulted in high fouling rates. However, no relationship exists between the percentage increase in the numbers of aerobic bacteria and the cycles of concentration at which the cooling tower was operated. These observations are supported by results from PLFA profiles that showed that the community structure within the planktonic and sessile samples of the experiments operated at low linear flow velocities were similar. The planktonic and sessile phases of these two experiments had similar levels of Gram-positive-, Gram-negative- bacteria and fungi. The community structure composition of the planktonic and sessile phases in the experiments operated at high linear flow velocities was also similar. PLFA analysis further demonstrated that the highest estimated viable biomass was in the experiment operated at a low linear flow velocity of 0.6 m/s. Shannon- Weaver index analysis of DGGE profiles (general structural diversity) also indicated that the planktonic bacterial diversity during operation at low linear flow velocities were the highest. Although scanning electron microscopy results illustrated that the planktonic and sessile microbial populations throughout the five experiments were generally similar. these results supported the observations of the other techniques. These techniques all supported the notion that corrosion rates may not be directly related to the total microbial biomass or the number of species on mild steel or stainless steel. Corrosion rates seem to be more profoundly affected by biofilm composition within the sessile phase. Based on the results obtained when using Primary Column Bottoms as cooling water, it were evident that variation in cycles of concentration and linear flow velocity had a significant effect (p>0.05) on the fouling, scaling and corrosion rates on mild steel corrosion coupons and heat exchanger tubes. Low linear flow velocities resulted in high fouling rates, increased bacterial numbers as well as high bacterial and fungal diversities. High cycles of concentration resulted in high scaling and corrosion rates and also had the result of similar community structure profiles. This research study could facilitate the selection of optimised operational parameters for the re-use of industrial process water (such as Primary Column Bottoms) as cooling water to minimise fouling, scaling and corrosion.
Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007

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Chavez, Jorge A., e Richard P. Korswagen. "COMPUESTOS CARBENICOS y SU IMPLICANCIA EN EL MECANISMO DEL PROCESO FISCHER-TROPSCH". Revista de Química, 2017. http://repositorio.pucp.edu.pe/index/handle/123456789/101202.

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Mediante el proceso Fischer-Tropsch es posible obtener, a partir del carbón, hidrocarburos que pueden ser utilizados como combustible. Como veremos más adelante,esta fue la razón del rápido desarrollo de este proceso.Los compuestos carbénicos son estudiados en los laboratorios de la SecciónQuímica de la Pontificia Universidad Católica del Perú, y siendo el procesoFischer-Tropsch el ejemplo de catálisis , heterogénea por excelencia,resulta interesante conocer su relación.El presente artículo es una pequeña introducción a la síntesis FischerTropsch. Debido a la complejidad y al gran número de puntos involucrados, tocaremos sólo los puntos más importantes con el fin de captar el interés sobre un tema que puede ser de importancia para el desarrollo del Perú.

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42

Petersen, Abdul Muhaymin. "Comparisons of the technical, financial risk and life cycle assessments of various processing options of sugercane bagasse to biofuels in South Africa". Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/20156.

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Thesis (MScEng)--Stellenbosch University, 2012
ENGLISH ABSTRACT: Through many years of research, a number of production schemes have been developed for converting lignocellulosic biomass into transport fuels. These technologies have been assessed through a number of techno-economic studies for application in a particular context in terms of the technical and economic feasibility. However, previous studies using these methods have tended to lack vigour in various aspects. Either the energy efficiency of the processes were not maximised through adequate heat integration, or a competing technology which existed was not considered. From an economic perspective, the financial models would often lack the vigour to account for the risk and uncertainty that is inherent in the market prices of the commodities. This phenomenon is especially relevant for the biofuel industry that faces the full fledge of uncertainties experienced by the agricultural sector and the energy sector. Furthermore, from an environmental perspective, the techno-economic studies had often ignored the environmental impacts that are associated with biofuel production. Thus, a comparative study could have favoured an option due to its economic feasibility, while it could have had serious environmental consequences. The aim of this study was to address these issues in a South African context, where biofuels could be produced from sugarcane bagasse. The first step would be to modify an existing simulation model for a bioethanol scenario that operates with a Separate Hydrolysis and Fermentation (SHF process) configuration into a second processing scenario that operates with a Simultaneous Saccharification and Fermentation (SSF process) configuration using reliable experimental data. The second step was to ensure that the maximum energy efficiency of each scenario was realised by carrying out pinch point analysis as a heat integration step. In contrast to these biological models is the thermochemical model that converts bagasse to gasoline and diesel via gasification, Fischer-Tropsch synthesis and refining (GFT process). While there were no significant advances in technology concerning this type of process, the energy efficiency was to be maximised with pinch point analysis. The GFT process obtained the highest energy efficiency of 50.6%. Without the affects of pinch point technology, the efficiency dropped to 46%, which thus emphasises the importance of heat integration. The SSF had an efficiency of 42.8%, which was superior to that of the SHF at 39.3%. This resulted from a higher conversion of biomass to ethanol in the SSF scenario. Comparing the SHF model to an identical model found in literature that did not have pinch point retrofits, this study showed lower efficiency. This arose because the previous study did not account for the energy demands of the cold utility systems such as the cooling tower operation, which has been shown in this study to account for 40% of the electrical energy needs. The economic viability of all three processes was assessed with Monte Carlo Simulations to account for the risks that the fluctuations in commodity prices and financial indices pose. This was accomplished by projecting the fluctuations of these parameters from samples of a historical database that has been transformed into a probability distribution function. The consequences were measured in terms of the Net Present Value (NPV) and Internal Rate of Return (IRR) for a large number of simulations. The results of these variables were aggregated and were then assessed by testing the probability that the NPV<0, and that the IRR recedes below the interest rate of 12.64%. The investment was thus deemed unfeasible if these probabilities were greater than 20%. Both biological models were deemed profitable in terms of this standard. The probabilities were 13% for the SSF and 14% for the SHF. The GFT process however was deemed completely unfeasible because the probability that the NPV<0 was 78%. Given that the GFT process had the highest energy efficiency, this result arises mainly because the capital investment of 140,000USD/MWHHV of biomass energy input is to enormous for any payback to be expected. The environmental footprint of each process was measured using Life Cycle Assessments (LCAs). LCAs are a scientifically intricate way of quantifying and qualifying the effects of a product or process within a specified boundary. The impacts are assessed on a range of environmental issues, such as Global Warming, Acidification, Eutrophication and Human toxicity. Furthermore, if the project under concern has multiple output products, then the impacts are distributed between the output products in proportion to the revenue that each generates. The impacts were either relative to the flow of feedstock, which was 600MW of bagasse, or to the functional unit, which was the amount of fuel required to power a standard vehicle for a distance of 1 kilometre. In either case, the GFT scenario was the least burdening on the environmental. This was expected because the GFT process had the highest energy efficiency and the process itself lacked the use of processing chemicals. Relative to the feedstock flow, the SSF was the most environmentally burdening scenario due to the intensive use of processing chemicals. Relative to the functional unit, the SHF was the most severe due to its low energy efficiency. Thus, the following conclusions were drawn from the study:  The GFT is the most energy and environmentally efficient process, but it showed no sign of economic feasibility. iv  There is no significant difference in the economic and environmental evaluation of the SSF and SHF process, even though the SSF is considered to be a newer and more efficient process. The major cause of this is because the setup of the SSF model was not optimised.
AFRIKAANSE OPSOMMING: Deur baie jare van navorsing is ‘n aantal produksie-skemas vir die omskakeling van lignosellulose biomassa na vloeibarebrandstof ontwikkel. Hierdie tegnologië is geassesseer ten opsigte van die tegniese en ekonomiese haalbaarheid deur middel van tegno-ekonomiese studies in bepaalde tekste. Tog het hierdie vorige studies besliste beperkings gehad. Of die energie-doeltreffendheid van die proses is nie gemaksimeer deur voldoende hitte-integrasie nie, of 'n mededingende tegnologie wat bestaan is nie oorweeg nie. Vanuit 'n ekonomiese perspektief, was die finansiële modelle dikwels nie die omvattend genoeg om rekening te hou met die risiko en onsekerheid wat inherent is in die markpryse van die kommoditeite nie. Hierdie verskynsel is veral relevant vir die biobrandstof bedryf wat die volle omvang van onsekerhede ervaar waaraan die landbousektor en die energiesektoronderhewig is. Verder het die tegno-ekonomiese studies dikwels die omgewingsimpakte wat verband hou met biobrandstofproduksie geïgnoreer. Dus kon ‘n opsie deur die ekonomiese haalbaarheid bevoordeel word, ten spyte van die ernstige omgewingsimpakte wat dit kon inhou. Die doel van hierdie studie was om hierdie kwessies aan te spreek in 'n Suid-Afrikaanse konteks, waar biobrandstof uit suikerriet bagasse geproduseer kan word. Die eerste stap was om 'n bestaande simulasiemodel vir 'n bio-scenario wat met Afsonderlike Hidroliese en Fermentasie (SHF proses) stappe werk, te modifiseer vir 'n tweede verwerking scenario wat met 'n gelyktydige Versuikering en Fermentasie (SSF proses) konfigurasie werk. Die verandering is gedoen deur die gebruik van betroubare eksperimentele data. Die tweede stap was om te verseker dat elke scenario die maksimum energie-doeltreffendheid het, deur 'n hitte-integrasie stap, wat gebruik maak van “pinch-point” analise. In teenstelling met hierdie biologiese modelle, is daar die thermochemiese roete waar petrol en diesel van bagasse vervaardig word via vergassing, Fischer-Tropsch-sintese en rafinering (GFT proses). Daar was geen betekenisvolle vooruitgang in tegnologie vir hierdie proses nie, maar die energie-doeltreffendheid is gemaksimeer word deur energie-integrasie. Die GFT proses toon die hoogste energie-doeltreffendheid van 50,6%. Sonder die invloed van energie-integrasie het die doeltreffendheid gedaal tot 46%, wat dus die belangrikheid van hitte-integrasie beklemtoon. Die SSF het 'n effektiwiteit van 42,8% gehad, wat beter was as dié 39,3% van die SHF opsie. Hierdie hoër effektiwiteit wasas gevolg van die hoër omskakeling van biomassa na etanol in die SSF scenario. Die energie doeltreffendheid vir die SHF-model was laer as met 'n identiese model (sonder energie-integrasie) wat in die literatuur gevind wat is. Dit het ontstaan omdat die vorige studie nie 'n volledig voorsiening gemaak het met die energie-eise van die verkillingstelselsnie, wat tot 40% van die elektriese energie behoeftes kan uitmaak. Die ekonomiese lewensvatbaarheid van al drie prosesse is bepaal met Monte Carlo simulasies om die risiko's wat die fluktuasies in kommoditeitspryse en finansiële indekse inhou, in berekening te bring. Hierdie is bereik deur die projeksie van die fluktuasies van hierdie parameters aan die hand van 'n historiese databasis wat omskep is in 'n waarskynlikheid verspreiding funksie. Die gevolge is gemeet in terme van die netto huidige waarde (NHW) en Interne Opbrengskoers (IOK) vir 'n groot aantal simulasies. Die resultate van hierdie veranderlikes is saamgevoeg en daarna, deur die toets van die waarskynlikheid dat die NPV <0, en dat die IRR laer as die rentekoers van 12,64% daal, beoordeel. Die belegging is dus nie realiseerbaar geag as die waarskynlikhede meer as 20% was nie. Beide biologieseprosesse kan as winsgewend beskou word in terme van bostaande norme. Die waarskynlikhede was 13% vir die SSF en 14% vir die SHF. Aangesien die NHW van die GFT-proses onder 0 met ‘n waarskynlikheid van 78% is, is die opsie as nie-winsgewend beskou. Gegewe dat die GFT-proses die hoogste energie-doeltreffendheid het, is die resultaat hoofsaaklik omdat die kapitale belegging van 140,000 USD / MWHHV-biomassa energie-inset te groot is, om enige terugbetaling te verwag. Die omgewingsvoetspoor van elke proses is bepaal deur die gebruik van Lewens Siklus Analises (“Life Cycle Assessments”) (LCAS). LCAS is 'n wetenskaplike metodeom die effek van ‘n produk of proses binne bepaalde grense beide kwalitatief en kwantitatief te bepaal. Die impakte word beoordeel vir 'n verskeidenheid van omgewingskwessies, soos aardverwarming, versuring, eutrofikasie en menslike toksisiteit. Voorts, indien die projek onder die saak verskeie afvoer produkte het, word die impakte tussen die afvoer produkte verdeel, in verhouding tot die inkomste wat elkeen genereer. Die impak was met of relatief tot die vloei van roumateriaal (600MW van bagasse), of tot die funksionele eenheid, wat die hoeveelheid van brandstof is om 'n standaard voertuig aan te dryf oor 'n afstand van 1 kilometer. In al die gevalle het die GFT scenario die laagste belading op die omgewing geplaas. Hierdie is te verwagte omdat die GFT proses die hoogste energie-doeltreffendheid het en die proses self nie enige addisionele chemikalieë vereis nie. Relatief tot die roumateriaal vloei, het die SSF die grootse belading op die omgewing geplaas as gevolg van die intensiewe gebruik van verwerkte chemikalieë. Relatief tot die funksionele eenheid, was die SHF die swakste as gevolg van sy lae energie-doeltreffendheid.

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Santos, Onelia Aparecida Andreo dos. "Sintese de Fischer-Tropsch em catalisadores de ferro". [s.n.], 1986. http://repositorio.unicamp.br/jspui/handle/REPOSIP/267078.

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Orientador: Mario de Jesus Mendes
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Campinas
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Resumo: A reação de síntese de Fischer - Tropsch tem merecido uma grande atenção pelo seu interesse tecnológico e científico. Naturalmente este interesse está, em grande parte, associado ao problema da escassez do petróleo, na medida em que a síntese de Fischer - Tropsch oferece uma rota adequada para a transformação de combustíveis sólidos em combustíveis líquidos e gasosos e em insumos básicos da industrIa petroquímica. Dada a estrutura do mercado brasileiro, este interesse está essencialmente dirigido para a substituição do óleo diesel e do óleo combustível. A experiência mostra que, através de uma seleção adequada do catalisador e das condições operatórias,é possível alterar, dentro de certos limites, a distribuição dos produtos obtidos na reação de síntese. Neste trabalho é apresentada uma discussão sobre a natureza dos catalisadores usados na síntese de Fischer-Tropsch, assim como o mecanismo da reação, com ênfase nos catalisadores à base de ferro. Pretende-se com esta discussão, identificar algumas possíveis vias para o desenvolvimento de catalisadores otimizados, mais ativos e mais seletivos, para determinadas frações de produtos (gasolina, diesel, olefinas, etc). É ainda apresentada uma descrição da instalação desenvolvida para a coleta de dados cinéticos na síntese de Fischer - Tropsch, e discutidas, com base em resultados preliminares, as dificuldades encontradas, em particular no que respeita à análise das misturas complexas obtidas como produto da reação.
Abstract: The Fischer-Tropsch synthesis reaction has received great attention due to its scientific and technological interest. This interest arises mostly in association with the dwindling of petroleum reserves, and because the Fischer - Tropsch synthesis offers an appropriate route for the transformation of solid fuels into liquid or gaseous fuels, as well as basic chemicals for the petrochemical industry. Considering the structure of the Brazilian market, this interest is essencially directed for the substitution of diesel and fuel oil. Accumulated experience with the synthesis reaction shows that it is possible to alter, within certain limits, the distribution of the products obtained. In this work a discussion is presented on the nature of the catalysts used in the Fischer - Tropsch synthesis, as well as on the reaction mechanism, with emphasis on catalysts based on iron. The aim of this discussion is to establish possible schemes for the development of optimized catalysts, with better activity and selectivity for desired product fractions(gasoline, diesel, olefins,etc). It is also presented the description of an experimental equipment developed for collecting kinetic data on the Fischer - Tropsch synthesis, and discussed the difficulties that were met in the preliminary tests, particularly with reference to chemical analysis of the products of reaction.
Mestrado
Mestre em Engenharia Química

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Porto, Luismar Marques. "Estudo de catalisadores de ferro fundido para a síntese Fischer-Tropsch". Florianópolis, SC, 1987. http://repositorio.ufsc.br/xmlui/handle/123456789/75437.

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Dissertação (mestrado) - Universidade Federal de Santa Catarina, Curso de Pós-Graduação em Físico-Química
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Hohwiller, Carole. "La production de carburants liquides par thermoconversion de biomasse lignocellulosique : évaluation pour le système énergétique français futur". Phd thesis, École Nationale Supérieure des Mines de Paris, 2011. http://pastel.archives-ouvertes.fr/pastel-00620639.

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La biomasse est appelée à représenter une part croissante de la consommation mondiale d'énergie primaire et la recherche de l'optimisation de l'usage d'une telle ressource, abondante mais pas pléthorique, s'impose. Cette thèse pose la question de la place, dans cette optimisation, des biocarburants de deuxième génération, en se focalisant sur la voie thermochimique, et plus particulièrement sur la synthèse de carburants liquides par le procédé Fischer-Tropsch qui permet d'obtenir des hydrocarbures du type naphta, kérosène et gazole. Pour traiter cette question, une démarche d'évaluation est proposée, qui comporte : - une évaluation à l'échelle des procédés, appliquée à une famille comportant au départ une centaine d'options, - une approche systémique pour évaluer l'insertion des procédés dans le système énergétique français futur. La mise en œuvre de cette démarche d'évaluation montre comment : - les procédés thermochimiques de production de biocarburants de deuxième génération permettent d'associer la biomasse et d'autres énergies primaires moins limitées pour maximiser le transfert de carbone renouvelable de la biomasse dans des carburants liquides, mais à des coûts qui restent élevés ; - la réponse à la question de l'optimisation de l'usage de la biomasse et de la place à donner aux biocarburants dépend fortement de l'évolution globale du système énergétique et de la faisabilité du stockage du CO2.

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Silva, Dagoberto de Oliveira. "Nanopartículas bimetálicas Co/Pt preparadas em líquidos iônicos e aplicação em processo Fischer-Tropsch". reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2013. http://hdl.handle.net/10183/85131.

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O presente trabalho descreve a síntese e caracterização de nanopartículas bimetálicas de cobalto e platina, estabilizadas por líquidos iônicos, para aplicação como catalisadores em reações de hidrogenação de monóxido de carbono (Reação Fischer-Tropsch) para produção de hidrocarbonetos. A formação das nanopartículas bimetálicas foi realizada pela hidrogenação dos precursores de cobalto (Cobaltoceno) e platina (Pt2dba3) dissolvidos em líquidos iônicos derivados do cátion imidazólio. A hidrogenação resultou em nanopartículas magnéticas de CoPt3 com tamanho médio de 7,3 nm utilizando o líquido iônico BMI.N(Tf)2 e nanopartículas magnéticas de CoPt3/Pt com tamanho médio de 7,2 nm utilizando o líquido iônico BMI.PF6. Análises de redução a temperatura programada comprovaram que a presença da platina diminuiu a temperatura de redução do cobalto. Para nanopartículas de CoPt3 a temperatura de redução foi de aproximadamente 215 °C enquanto que para as nanopartículas de CoPt3/Pt a temperatura de redução foi de aproximadamente 125 °C. Os testes catalíticos para reações de FT foram realizados utilizando uma célula de DRIFT (Harrick high temperature reaction chamber) como reator batelada, com pressão constante de 20 bar de uma mistura padrão de hidrogênio e monóxido de carbono (H2/CO = 2/1) e temperatura de 230 °C. As análises por espectroscopia no infravermelho foram realizadas após 16 h de reação, e os produtos formados foram analisados por cromatografia gasosa. As análises por cromatografia apresentaram distribuição de produtos diferentes entre as nanopartículas. A distribuição de produtos formados na reação FT, utilizando nanopartículas de CoPt3, apresentou 70% de hidrocarbonetos pesados (a1 = 0,52, a2 = 0,72). Utilizando as nanopartículas de CoPt3/Pt a formação de hidrocarbonetos pesados foi de apenas 44% (a1 = 0,60, a2 = 0,67) A maior quantidade de produtos leves foi atribuída ao mecanismo de reação via inserção de carbenos, favorecido pela maior quantidade de platina em nanopartículas de CoPt3/Pt. A presença de carbenos na superfície do catalisador foi compravada por análises de espectroscopia no infravermelho após 16h de reação. Estudos de cinética transiente comprovaram a formação de espécies ativas de carbono na superfície das nanopartículas logo no início da reação, porém as nanopartículas de CoPt3/Pt exibiram um processo lento de ativação quando comparadas as nanopartículas de CoPt3. Para ambos os casos a obtenção das condições para o estado-estacionário da reação foram alcançadas em aproximadamente 40 min de reação. Portanto, foi comprovado que a platina diminui a temperatura de redução do cobalto em nanopartículas bimetálicas. Também pôde-se observar que a platina favorece o mecanismo via inserção de carbenos na reação FT aumentando a quantidade de produtos leves.
This work describes the synthesis and characterization of cobalt and platinum bimetallic nanoparticles stabilized by ionic liquid for the synthesis of hydrocarbons by Fischer Tropsch reaction. The formation of bimetallic nanoparticles was performed by hydrogenation of cobalt and platinum precursors (cobaltocene and Pt2dba3) dissolved in imidazolium ionic liquids. The hydrogenation resulted in magnetic CoPt3 nanoparticles with average size of 7.3 nm when BMI.N(Tf)2 was used and magnetic CoPt3/Pt nanoparticles with average size of 7.2 nm when using BMI.PF6. The results from temperature programmed reduction analysis indicated that the platinum appreciably lowered the reduction temperature of cobalt. For CoPt3 nanoparticles the reduction temperature was approximately 215 °C and for CoPt3/Pt nanoparticles the reduction temperature was approximately 125°C. Catalytic tests for the Fischer-Tropsch reaction were performed using a DRIFT cell (Harrick high temperature reaction chamber) as a batch reactor under controlled temperature and constant pressure (20 bar of a H2/CO mixture, 2/1 molar ratio). The infrared analysis was performed after 16 h of reaction, and the products were analyzed by gas chromatography (GC). The GC results showed different product distributions and different growth probability for the nanoparticles. The use of CoPt3 nanoparticles resulted in the formation of 70% of C11+ hydrocarbons (a1 = 0.52, a2 = 0.72). When using CoPt3/Pt, the formation was only 44% of C11+ hydrocarbons (a1 = 0.60, a2 = 0.67). These differences of product distributions were attributed to favor carbene insertion mechanism when using CoPt3/Pt nanoparticles in FT reaction. The chemical transient kinetics analysis proved the formation of atomic carbon reactive species on metal surfaces of both nanoparticles. However CoPt3/Pt nanoparticles presented a slow activation process when compared with CoPt3. The conditions for steady-state were achieved in approximately 40 min of FT reaction for both nanoparticles. Therefore, the presence of platinum appreciably lowered the reduction of cobalt in bimetallic nanoparticles and favor the carbene insertion mechanism in FT reaction.

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47

Freitas, Antonio Carlos Daltro de 1986. "Análise termodinâmica da transformação de biomassa em combustíveis utilizando técnicas de otimização global". [s.n.], 2015. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266028.

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Orientador: Reginaldo Guirardello
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: Há um crescente interesse por fontes alternativas de energia limpa, segura e renovável, e por tecnologias de transformação destas fontes em combustíveis. Dentre esses processos, a reação de gaseificação utilizando água supercrítica (SCWG), visando a produção de hidrogênio e a reação de síntese de Fischer-Tropsch (FT) visando a produção de combustíveis líquidos, vêm ocupando papel de destaque. Nesse contexto, essa tese teve como objetivo realizar a análise termodinâmica das reações envolvidas na transformação de biomassa em combustíveis, utilizando para isso, técnicas de otimização global. Foram aplicadas as metodologias de minimização da energia de Gibbs para sistemas com pressão e temperatura constantes e de maximização da entropia para sistemas com pressão e entalpia constantes. Os problemas foram formulados na forma de programações lineares e não lineares, e as metodologias propostas foram implementadas e resolvidas no software GAMS. Primeiramente foi realizada a análise termodinâmica da transformação de diferentes fontes renováveis de energia, tais como etanol, glicerol, glicose, celulose, lignina, bagaço de cana de açúcar e biomassa microalgal, em hidrogênio ou gás de síntese por meio da reação de SCWG. Posteriormente o uso do gás de síntese produzido, foi termodinamicamente avaliado visando a produção de combustíveis líquidos, por meio da reação de síntese de Fischer-Tropsch. Com esse trabalho, contribuímos com uma maior elucidação das condições reacionais mais favoráveis para cada um dos processos analisados, estudando ainda estratégias para se obter uma maior conversão dos reagentes e aumentar a produtividade dos compostos de interesse, além de verificar o comportamento energético dos sistemas associados
Abstract: There is a growing interest in alternative sources of clean, safe and renewable energy, and in technologies for processing these sources into fuels. Among these processes, the supercritical water gasification (SCWG) reaction, for hydrogen production, and the Fischer-Tropsch (FT) synthesis reaction, for liquid fuels production, have occupied a prominent role. In this context, this thesis performed the thermodynamic analysis of reactions involved in the transformation of biomass into fuels, using for it, global optimization techniques. Methodologies are applied to minimize Gibbs energy, in systems with constant pressure and temperature, and maximize the entropy, in systems with constant pressure and enthalpy. The problems are formulated in the form of linear and nonlinear programming, and the proposed methodologies are implemented and solved in the software GAMS. The thermodynamic analysis of the transformation of different sources such as ethanol, glycerol, glucose, cellulose, lignin, sugarcane bagasse and microalgal biomass in hydrogen or syngas, through the SCWG reaction are performed first. Later, the use of syngas produced are thermodynamically evaluated for the production of liquid fuels by the Fischer-Tropsch synthesis reaction. With this work we contribute to a further elucidation of the more favorable reaction conditions for each of the cases examined, also considering strategies to increase the conversion of reactants and the productivity of the desired products, as well as the realization of the energy characterization of the processe
Doutorado
Engenharia Química
Doutor em Engenharia Química

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48

BEZERRA, Victor Vital Leão. "Síntese de Fischer-Tropsch sobre catalisadores convencionais e estruturado para obtenção de combustíveis líquidos". Universidade Federal de Pernambuco, 2015. https://repositorio.ufpe.br/handle/123456789/16895.

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PRH-28 / ANP
Como principal reação da tecnologia Gas-to-Liquids (GTL), a síntese de Fischer-Tropsch (SFT) surge como alternativa expoente para enriquecimento da cadeia do gás natural. Utilizando uma unidade de bancada que possibilita a reação e a análise dos produtos formados, foram realizadas reações a pressão constante de 2,0 MPa e relação molar de gás de síntese H2:CO=2:1. Foi investigado o uso de catalisadores sólidos, não promovido (20%Co/γ-Al2O3) e promovido (0,5%Pt-20%Co/γ-Al2O3) e um sistema estruturado (0,5%Pt-20%Co/γ-Al2O3-micromonólito), observando a influência da temperatura (185 a 230ºC) e velocidade espacial (0,3 a 1,2 mol.gcat-1.h-1). Constatou-se que nas reações da SFT ao se utilizar o catalisador Co/γ-Al2O3, nas condições operacionais de temperatura e velocidade espacial investigadas, foram obtidas variações na conversão de CO (3,4 a 56%), e nas seletividades de CH4 (4,4 a 23,5%); de CO2 (1,1 a 3,0%); de C2-C4 (0,8 a 2,7%) e de C5+ (76,5 a 95,6%), e uma probabilidade de crescimento da cadeia (α) de 0,81 a 0,94. Para o catalisador Co-Pt/γ-Al2O3, em diferentes condições operacionais de temperatura e velocidade espacial, foram obtidas variações na conversão de CO (3,7 a 99,8 %), e nas seletividades de CH4 (3,7 a 23,8%); de CO2 de (0,7 a 11,0 %); de C2-C4 de (1,1 a 4,4%) e de C5+ (71,9 a 95,2%), e uma probabilidade de crescimento da cadeia (α) de 0,79 a 0,93. A adição da platina não alterou a estrutura do catalisador, mas favoreceu na redução dos óxidos de cobalto. Observou-se que para todos os catalisadores investigados neste trabalho, o aumento da temperatura acarretou um aumentou na conversão de CO, entretanto favoreceu a formação de metano. A diminuição da velocidade espacial, de modo geral, acarretou em um aumento na conversão de CO. Quando comparados os catalisadores sólidos, nas mesmas condições operacionais, o catalisador promovido por platina apresentou uma maior atividade catalítica. Quando comparado o catalisador estruturado com o catalisador sólido, não houve grande diferença na atividade catalítica, entretanto o catalisador estruturado apresentou uma maior afinidade para formação e C5+. O sistema estruturado apresentou um excelente controle na dispersão do calor formado na reação.
As main reaction technology Gas-to-Liquids (GTL), the Fischer-Tropsch synthesis appears as an alternative to valorize the natural gas chain. Using a bench unit, reactions were carried out at constant pressure of 2.0 MPa, molar ratio syngas H2:CO=2:1. It was investigated the use of solid catalysts, not promoted (20%Co/γ-Al2O3) and promoted (0,5%Pt-20%Co/γ-Al2O3) and a structured system (0,5%Pt-20%Co/γ-Al2O3-micromonolite). The influence of temperatures (185 to 230°C) and space velocity (0,3 to 1,2 mol.gcat-1.h-1) were studied. It was found that in the FTS reactions, using the catalyst Co/γ-Al2O3 in operating conditions of temperature and space velocity investigated variants were obtained in CO conversion from 3.4 to 56%, and the selectivity to CH4 4.4 to 23,5%; CO2 1,1 to 3,0%; C2-C4 0,8 to 2,7% and the C5+ from 76,5 to 95,6%, and the chain growth probability (α) 0,81 to 0,94. Results of the Pt-Co/γ-Al2O3 show CO conversion from 3,7 to 99,8% were obtained, and the selectivity from CH4 3,7 to 23, 8%; CO2 0,7 to 11,0%; C2-C4 1,1 to 4,4% C5+ from 71,9 to 95,2%, and the chain growth probability (α) from 0.79 to 0,93. The addition of platinum not altering the structure of the catalyst, but favored in the reduction of cobalt oxides. It was observed that for all catalysts studied in this work, the increase in temperature led an increased of CO conversion, however favored the formation of methane. The reduction of space velocity, generally, resulted in an increase of CO conversion. When comparing the solid catalysts, under the same operating conditions, the catalyst promoted by platinum showed higher catalytic activity. The structured catalyst when compared with the solid catalyst, did not differences in catalytic activity, however, the structured catalyst had a higher affinity for formation for C5+. The structured system showed excellent control in heat dispersion formed in the reaction.

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49

Silva, Dagoberto de Oliveira. "Nanopartículas de cobalto preparadas em líquidos iônicos: síntese, caracterização e aplicação em processo Fischer-Tropsch". reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2008. http://hdl.handle.net/10183/14350.

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O presente trabalho descreve a síntese e caracterização de nanopartículas de cobalto estabilizadas por líquidos iônicos e a aplicação das mesmas como catalisadores em reações de hidrogenação de monóxido de carbono para produção de hidrocarbonetos. A síntese de hidrocarbonetos via monóxido de carbono e hidrogênio, conhecida como processo Fischer-Tropsch, vem sendo muito estudada para produção de diesel e bases de lubrificantes, pois é uma excelente opção como fonte alternativa de combustível. A formação de nanopartículas de cobalto foi realizada pela simples decomposição térmica de precursores de cobalto carbonila dissolvidos em líquidos iônicos derivados do cátion imidazólio. A decomposição resultou em nanopartículas magnéticas com tamanho médio de 4,5; 5,2; 7,7 e 10,7 nm para os líquidos iônicos BMI.BF4, DMI.BF4, BMI.N(Tf)2 e TDMI.N(Tf)2, respectivamente. Os testes catalíticos para reações de Fischer-Tropsch foram realizados utilizando uma célula de DRIFT (Harrick high temperature reaction chamber) como reator batelada, com monitoração da temperatura e pressão constante de 20 bar de uma mistura padrão de hidrogênio e monóxido de carbono (H2/CO = 2/1), a reação foi monitorada por infravermelho e os produtos formados foram extraídos com solvente orgânico e analisados por cromatografia gasosa. Observou-se misturas de hidrocarbonetos (C7 a C30), com alta probabilidade de crescimento da cadeia (ASF). Estudos encontrados na literatura relatam que nanopartículas com diâmetro de 5 a 8 nm, são ideais para catalisadores aplicados em processo Fischer-Tropsch. As análises de propriedades magnéticas mostraram que as nanopartículas apresentaram propriedades de superparamagnetismo, caracterísctico de partículas com momodomínio, e possuem grande potencial para aplicação em materiais de gravação magnética. Portanto, líquidos iônicos demonstraram excelentes propriedades de agentes estabilizantes para a síntese destes nanocatalisadores de cobalto, além de possuírem boas perspectivas de atuarem como suportes para as nanopartículas a serem utilizadas com catalisadores em procesos realizados em reatores contínuos.
This work describes the synthesis and characterization of ionic liquid stabilized cobalt nanoparticles and their application as catalysts for hydrocarbon synthesis from carbon monoxide. The synthesis of hydrocarbons using hydrogen and carbon monoxide, known as Fischer-Tropsch process, has been studied and employed for the production of fuels and lubricants. The formation of cobalt nanoparticles was performed by the simple thermal decomposition of the carbonyl cobalt precursors dissolved in imidazolium ionic liquids. The decomposition resulted in magnetic nanoparticles with average sizes of 4.5; 5.2; 7.7 and 10.7 nm for BMI.BF4, DMI.BF4, BMI.N(Tf)2 and TDMI.N(Tf)2 ionic liquids respectively. Catalytic tests were performed for the Fischer-Tropsch reaction using a DRIFT cell (Harrick high temperature reaction chamber) as a batch reactor with temperature control and constant pressure (20 bar of a H2/CO mixture, 2/1 molar ratio), and monitored by IR spectroscopy. The products were extracted with organic solvents and analyzed by GC. Anderson-Shulz-Flory parameter (ASF) indicated high chain growth probability for the hydrocarbon mixtures (C7 to C30) obtained. Previous studies show that nanoparticles with diameters of 5 to 8 nm are ideal for catalysts applied to the Fischer-Tropsch synthesis. The analysis of the magnetic properties showed that the nanoparticles formed present superparamagnetism, characteristic of monodomain particles. These nanoparticles present great potential for applications in magnetic recording materials. Therefore, ionic liquids showed excellent properties as stabilizing agents for the synthesis of these cobalt nanocatalysts. Moreover they are promising nanoparticle supports for the application as catalysts in slurry reactor processes.

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50

Freitas, Antonio Carlos Daltro de 1986. "Análise termodinâmica de processos de reforma do metano e da síntese Fischer-Tropsch". [s.n.], 2012. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266746.

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Orientador: Reginaldo Guirardello
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: As reações de reforma de hidrocarbonetos leves, especialmente o gás natural, são reações químicas de elevada importância e representam etapas chave para a produção em larga escala de hidrogênio, para uso em reações de hidrogenação ou em células a combustível, ou de gás de síntese para aplicação na produção de amônia, metanol ou ainda para a síntese de Fischer-Tropsch (FT). A síntese de Fischer-Tropsch e o principal processo de conversao de hidrocarbonetos leves, como o metano, em hidrocarbonetos maiores, de maior valor agregado, assim a determinação das condições termodinamicamente favoráveis para a operação deste tipo de processos se torna cada vez mais necessária. Dentro desse contexto, as reações de reforma a vapor, reforma oxidativa, reforma autotérmica, reforma seca, reforma seca autotérmica e reforma seca combinada com reforma a vapor foram termodinamicamente avaliadas com o objetivo de determinar as melhores condições de reação para a produção de gás de síntese e de hidrogênio. Posteriormente, o gás de síntese produzido foi utilizado para a produção de metanol, etanol e hidrocarbonetos lineares, sendo avaliadas as melhores estratégias para a produção de cada um desses compostos. Para isso foram utilizadas as metodologias de minimização da energia de Gibbs a pressão e temperatura constantes e de maximização da entropia a pressão e entalpia constantes. Ambos os casos foram formulados como problemas de otimização na forma de programação não-linear, e resolvidas com o solver CONOPT2 do software GAMS 23.1'MARCA REGISTRADA'. A partir dos resultados obtidos com a aplicação da metodologia de minimização da energia de Gibbs, verificou-se que todos os processos de reforma avaliados se mostraram favoráveis para a produção de hidrogênio e/ou de gás de síntese do ponto de vista termodinâmico. Tendo a reação de reforma a vapor se destacado para a produção de hidrogênio devido a elevada razao molar H2/CO obtida no produto. A reação de oxidação parcial mostrou bons resultados para a produção de gás de síntese, devido a razão molar H2/CO próxima de 2 no produto. A comparação com dados experimentais permitiu verificar que a metodologia de minimização da energia de Gibbs apresentou boa capacidade de predição e pela comparação com dados simulados obtidos na literatura, pode-se verificar que a metodologia utilizada pelo presente trabalho esta de acordo com os dados publicados. Os resultados obtidos com a aplicação da metodologia de maximização da entropia pode-se verificar que as reações de reforma oxidativa, reforma autotérmica e reforma seca autotérmica, apresentaram comportamento autotérmico, tanto para o uso de O2 como para o uso de ar como agente oxidante. O ar mostrou capacidade de diminuir a elevação da temperatura final do sistema, sendo seu uso promissor para evitar pontos quentes no reator. A comparação com dados de perfil térmico de reatores, para as reações de reforma oxidativa e reforma autotérmica, únicas obtidas na literatura, demonstraram a boa capacidade de predição da metodologia de maximização da entropia para determinação das temperaturas de equilíbrio das reações. As analises realizadas pela aplicação da metodologia de minimização da energia de Gibbs para as reações de síntese de metanol, etanol e hidrocarbonetos lineares, demonstraram a viabilidade da produção desses compostos. Todas reações de síntese avaliadas apresentaram grande dependência da influencia do catalisador (efeito cinético) para promover a produção dos produtos de interesse. Aplicando-se a metodologia de maximização da entropia foi possível determinar que todas as reações de síntese apresentaram comportamento exotérmico. As metodologias empregadas, bem como o solver CONOPT2 aplicado no software GAMS® 23.1 se mostraram rápidos e eficazes para a solução dos problemas propostos, com baixos tempos computacionais para todos os casos analisados
Abstract: The reactions of reforming of light hydrocarbons, especially natural gas, are chemical reactions of great importance and represent key steps for large scale production of hydrogen for use in hydrogenation reactions or fuel cells, or synthesis gas production, for application in the ammonia or methanol production, or to Fischer-Tropsch (FT) synthesis. The Fischer- Tropsch synthesis is the main process of converting light hydrocarbons such as methane, in hydrocarbons of higher value added. The determination of the thermodynamically favorable conditions for the operation for this type of process is required. Within this context, the reactions of steam reforming, oxidative reforming, autothermal reforming, dry reforming, dry autothermal reforming and dry reforming combined with steam reforming were thermodynamically evaluated to determine the best reaction conditions for the production of synthesis gas and hydrogen. For this, we used the methods of Gibbs energy minimization, at constant pressure and temperature, and the Entropy maximization, at constant pressure and enthalpy. Both cases were formulated as optimization problems in the form of non-linear programming and solved with the software GAMS 2.5® with the solver CONOPT2. The results obtained by the method of minimization of Gibbs energy, for all the reform processes evaluated, proved able to produce hydrogen and syngas. Since the reaction of steam reforming showed greater ability to hydrogen production, due to high H2/CO molar ratio obtained in the product. The partial oxidation reaction showed good results for the syngas production, due to H2/CO molar ratio close to 2 in the product. The comparison with experimental data has shown that the Gibbs energy minimization method showed good predictive ability. By comparison with simulated data from the literature we can see that the methodology of minimization of Gibbs energy, used in this work is in agreement with data obtained in the literature for the same methodology. The results obtained using the methodology of entropy maximization allowed us to verify that the reactions of partial oxidation, autothermal reforming and dry autothermal reforming had autothermal behavior, both for the use of O2 as for the use of air as oxidizing agent. The air has shown ability to reduce the final temperature rise of the system, and its use has proved interesting to avoid hot spots in the reactor. A comparison with data from the reactor's thermal profile, for the reactions of partial oxidation and autothermal reforming, only found in the literature, showed good predictive ability of the methodology of entropy maximization to determine the final temperature of the reaction. The analysis realized using the methodology of Gibbs energy minimization for the synthesis reactions of methanol, ethanol and linear hydrocarbons, demonstrated the feasibility of producing these compounds. All synthesis reactions evaluated were greatly dependent on the influence of the catalyst (kinetic effect) to promote the production of products of interest. Trough the entropy maximization method was determined that all synthesis reactions analyzed presents exothermic behavior, but in the reaction conditions evaluated here, these systems can be considered safe. The methodologies used and applied in the software GAMS ® 23.1, and solved with the solver CONOPT2 proved to be fast and effective for solving the proposed problems with low computational time in all cases analyzed
Mestrado
Desenvolvimento de Processos Químicos
Mestre em Engenharia Química

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