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Biomass-to-liquids: uma contribuição ao estudo da obtenção de biocombustíveis sintéticos através da síntese Fischer-Tropsch / Biomass-to-liquids: a contribution to the synthetic biofuels obtaining study through Fischer-Tropsch synthesisAires Duarte 03 February 2009 (has links)
Pretende-se estudar um caminho alternativo para a obtenção de biocombustíveis sintéticos, para uso veicular, utilizando-se para tal a rota tecnológica conhecida como Biomass-to-Liquids (BTL) que consiste na utilização da síntese Fischer-Tropsch para a construção de cadeias de hidrocarbonetos a partir de unidades monoméricas obtidas de uma mistura gasosa majoritariamente formada por monóxido de carbono (CO) e hidrogênio (H), conhecida como syngas quando proveniente de fontes energéticas fósseis como o carvão mineral ou o gás natural ou também biosyngas quando proveniente de matéria-prima carbonada renovável, como é o caso da biomassa. O presente trabalho visa abordar o começo dessa cadeia produtiva ao introduzir um conceito para biomassa e os meios para obtenção do biosyngas através do processo conhecido como gaseificação; é feita uma menção à obtenção bem sucedida de biosyngas nas dependências do Instituto de Pesquisas Tecnológicas (IPT) de São Paulo. Segue-se com a utilização desse insumo na síntese Fischer-Tropsch largamente utilizada ao longo do século XX em países específicos para abastecimento da frota veicular local onde seu princípio fundamental é introduzido, assim como os principais mecanismos de formação de cadeias de hidrocarbonetos de diferentes pesos moleculares permitindo assim a obtenção de gasolina e óleo diesel. Essa dissertação apresenta conceitos para a palavra combustível, da mesma forma que introduz os combustíveis fósseis, seus importantes derivados e suas propriedades gerais para que seja possível, adiante, utilizá-los como comparativo com os biocombustíveis sintéticos; é apresentada a evolução histórica dessa tecnologia e são também abordadas a primeira e segunda gerações de biocombustíveis, para se trazer dados que indiquem as vantagens do óleo diesel Fischer-Tropsch quando comparado com seu equivalente oriundo da petroquímica convencional e por fim demonstrar sua superior qualidade sócio-ambiental como biocombustível sintético para o futuro da matriz energética mundial. / What is supposed to be on board of this study consists in an alternative way focused on vehicular use synthetic fuels obtaining, using as main process the technological route known as Biomass-to-Liquids (BTL), which one consists on Fischer-Tropsch synthesis use for hydrocarbons chain building starting from monomer units obtained from a gas mixture made up mostly by carbon monoxide (CO) and hydrogen (H), known as syngas from fossil energy sources such as coal or natural gas or also biosyngas from carbonaceous renewable raw materials, such as biomass. This paper aims to address the beginning of the production chain in order to introduce a concept for biomass and the biosyngas obtaining means through the process known as gasification, a reference is made to a successful biosyngas obtaining the dependencies at the Institute for Technological Research (IPT) from Sao Paulo. Then there is the use of that input in the Fischer-Tropsch synthesis widely used throughout the twentieth century, in specific countries, to supply the local vehicle fleet where its basic principle is introduced, as well as the main hydrocarbons chain formation mechanisms thus different molecular weights providing gasoline and diesel oil. This essay presents concepts for the word fuel, the same way that makes it for fossil fuels, their major products and their properties in order to use them as a comparison standard for synthetic biofuels, it was also presented the historical development of this technology and first and second generation of biofuels, in order to bring evidence to suggest the benefits of the Fischer-Tropsch diesel fuel once compared to its conventional equivalent come from the petrochemical and finally to demonstrate it as a socio-environmentally superior quality synthetic biofuel for the future of global energy matrix.
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EstimaÃÃo de parÃmetros, modelagem e simulaÃÃo da sÃntese de Fischer-Tropsch em reator tubular de leito fixo com catalisador de cobalto. / Parameters estimation, modeling and simulation of Fischer-Tropsch synthesis in fixed-bed tubular reactor with cobalt catalystAntonino Fontenelle Barros Junior 01 March 2013 (has links)
A reaÃÃo de sÃntese de Fischer-Tropsch, que pode ser compreendida como uma polimerizaÃÃo entre os gases monÃxido de carbono e hidrogÃnio, mistura conhecida por gÃs de sÃntese, com a formaÃÃo de hidrocarbonetos parafÃnicos e olefÃnicos, ocorre na presenÃa de catalisadores heterogÃneos, onde aqueles de cobalto aparecem como os mais promissores quando se deseja produzir fraÃÃes de hidrocarbonetos comercialmente mais favorÃveis, como gasolina, diesel e graxas. A reaÃÃo jà à encarada como alternativa ao petrÃleo, pois o gÃs de sÃntese à gerado a partir de outras fontes, notadamente o gÃs natural. O conhecimento da reaÃÃo ainda à fundamentalmente experimental, e nÃo existem mecanismos especÃficos que expliquem com exatidÃo a formaÃÃo dos produtos e sua distribuiÃÃo ao longo de uma faixa de hidrocarbonetos. Esse trabalho realiza inicialmente uma estimaÃÃo de parÃmetros, enquadrados em uma modelagem cinÃtica, que procuram explicar o desenvolvimento da reaÃÃo e a formaÃÃo das parafinas e olefinas em reatores tubulares de leito fixo com catalisadores de cobalto. De posse dos parÃmetros, procurou-se um modelo matemÃtico mais adequado à operaÃÃo do reator tubular, com a utilizaÃÃo de equaÃÃes para a transferÃncia de massa e de calor. Essas simulaÃÃes foram submetidas posteriormente a uma anÃlise estatÃstica para a determinaÃÃo de variÃveis mais significativas para a reaÃÃo. / In this work, the reaction of the Fischer-Tropsch synthesis, which may be understood as a polymerization between the gases carbon monoxide and hydrogen, mixture known as synthesis gas, with the formation of paraffinic and olefinic hydrocarbons, occurs under heterogeneous catalysis, where those of cobalt appear as the most promising when you want to produce hydrocarbon fractions commercially more favorable, such as gasoline, diesel and waxes. The reaction is already perceived as an alternative to petroleum, since the synthesis gas is generated from other sources, notably natural gas. The knowledge of the reaction is still essentially experimental, and there are no specific mechanisms that explain precisely the formation of the products and their distribution over a range of hydrocarbons. This work performs initial parameter estimation, framed in a kinetic modeling, which seek to explain the development of the reaction and the formation of paraffins and olefins in tubular fixed bed reactors with cobalt catalyst. In possession of the parameters, we tried to one better suited to reality modeling of reactor operation, with the use of equations for mass transfer and heat. These simulations were later subjected to a statistical analysis to determine the most significant variables for the reaction.
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Biomass gasification and catalytic conversion of synthesis gas:characterisation of cobalt catalysts for Fischer-Tropsch synthesisRomar, H. (Henrik) 02 May 2015 (has links)
Abstract
Biomass gasification as a thermochemical treatment method is typically used for heat and power production. Instead of burning the producer gas, it can be converted to added-value products, i.e to fuels and chemicals. One such conversion is the catalytic Fischer-Tropsch synthesis (FTS) which converts synthesis gas to a chain of aliphatic hydrocarbons (FT diesel) as studied in this thesis. This requires, however, proper cleaning steps of producer gas, such as the removal of tar compounds and other impurities. These cleaning steps are not considered in this thesis.
The first goal of the thesis was to determine the tar content in the producer gas from a small scale biomass gasifier. This subject is discussed in Paper I. The second and main goal of the thesis was the preparation and characterization of cobalt (or iron) catalysts for catalytic conversion of a gas mixture close to the synthesis as discussed in Papers II-V. The overall aim of the second part was to study the effects of promoters on the reducibility of cobalt and the effects of different calcination conditions on the degree of reduction and size of the metallic cobalt particles. In this later part different catalytic supports were used.
According to the results of the thesis, naphthalene and toluene were the main tar compounds in the producer gas representing almost 80 % of the GC detected tar compounds. Only traces of polycyclic aromatic compounds were detected and no phenolic compounds were found in the gas.
Further, a number of supported heterogeneous catalysts for FTS using cobalt (Co) or in some cases iron (Fe) as the active metal were prepared and characterized. These catalysts were supported on alumina (Al2O3), titanium dioxide (TiO2) or silicon carbide (SiC). Catalysts were promoted with Ru, Re or Rh in the concentrations of 0, 0.2, 0.5, and 1.0 mass-%. Several characterization methods (such as H2-TPR, catalytic activity measurements, N2 physisorption, CO chemisorption, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD)) were used to find answers to the behaviour of these catalysts under selected conditions and in the model reaction of FTS.
Based on the results, there are significant differences in the characteristics of the catalysts, the differences are dependent of the supports used, promoters added and calcination conditions used. The properties of the support, especially the pore size distribution will effect the distribution of products formed in the Fischer-Tropsch synthesis. Addition of promoters and variatons in calcination conditions will effect the dispersion and the particle size of the active metal. / Tiivistelmä
Biomassan kaasutus on termokemiallinen prosessi, jota käytetään pääosin sähkön- ja lämmöntuotannossa. Polton sijaan kaasutuksessa muodostuva synteesikaasu voidaan puhdistaa ja hyödyntää edelleen katalyyttisesti polttoaineiden ja kemikaalien valmistuksessa. Eräs mahdollisuus synteesikaasun hyödyntämiseen on Fischer-Tropsch synteesi (FTS), jossa koboltti- tai rautakatayyteillä voidaan tuottaa alifaattisia hiilivetyketjuja (FT-dieseliä), mitä on tutkittu tässä työssä. FT-synteesi vaatii kuitenkin puhtaan tuotekaasun ja sen vuoksi tervayhdisteet ja muut epäpuhtaudet on poistettava kaasusta. Kaasun puhdistusta ei ole kuitenkaan tutkittu tässä työssä.
Työn ensimmäisenä tavoitteena oli määrittää biomassan kaasutuksessa käytettävän pienikokoisen myötävirtakaasuttimen kaasun koostumus ja tervayhdisteet ja niiden pitoisuudet (julkaisu I). Toisena, ja tämän työn päätavoitteena oli Fischer-Tropsch -synteesissä käytettävien koboltti- ja rautakatalyyttien valmistus ja karakterisointi sekä käyttö synteesikaasun katalyyttisessä konvertoinnissa (julkaisut II-V). Erityisesti tutkittiin promoottorimetallien ja kalsinointiolosuhteiden vaikutusta koboltin pelkistymiseen ja kobolttimetallipartikkelien kokoon. Lisäksi tutkittiin ja vertailtiin erilaisia tukiaineita.
Työn tulosten perusteella naftaleiini ja tolueeni olivat pääasialliset tervayhdisteet myötävirtakaasuttimen tuotekaasussa ja niiden osuus oli yli 80 % kaasukromatografisesti havaittavista tervayhdisteistä. Lisäksi havaittiin pieniä määriä polysyklisiä aromaattisia yhdisteitä, kun taas fenolisia yhdisteitä ei havaittu tuotekaasussa.
Työssä valmistettiin ja karakterisoitiin lukuisa määrä erilaisia FT-katalyyttejä, joissa aktiivisena metallina oli koboltti tai rauta. Katalyyteissä tukiaineena oli alumiinioksidi (Al2O3), titaanidioksidi (TiO2) tai piikarbidi (SiC) ja promoottorimetallina joko Ru, Re tai Rh (pitoisuudet 0, 0.2 tai 1.0 massa-%). Katalyyttien karakterisointiin käytettiin useita menetelmiä, kuten H2-TPR, N2-adsorptio, CO-kemisorptio, XPS, XRD ja lisäksi määritettiin katalyyttien aktiivisuus ja selektiivisyys valituissa olosuhteissa FT-synteesin mallireaktioissa.
Tulosten perusteella katalyyttien välillä havaittiin selkeitä eroja riippuen käytetystä tukiaineesta, promoottorista ja kalsinointiolosuhteista. Tukiaineen ominaisuudet, erityisesti huokoskokojakauma vaikuttavat FT-synteesin tuotejakaumaan. Promoottorien lisäys katalyyttiin sekä kalsinointiolosuhteet vaikuttavat lisäksi dispersioon ja aktiivisen metallien partikkelikokoon.
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Development of a modern catalytic system for the production of C3+ aliphatic alcohols by the Fischer-Tropsch methodGanesan, Aravind January 2019 (has links)
This thesis deals with converting a mixture of H2 and CO, also referred to as syngas or producer gas, to higher or mixed alcohols and other fuels through a process called Fischer Tropsch Synthesis (FTS). It is a beneficial pathway that minimizes the dependence on oil and similar fossil fuels which contribute to rapid climate change by releasing harmful greenhouse gases. The syngas used in FTS, is generally obtained through gasification of biomass to make the entire process renewable and to make the resulting fuel carbon neutral. The products are pure due to prior cleaning of syngas mixture to remove oxides of nitrogen, sulphur and other particulate matter, before the process, thereby drastically reducing the net exhaust gas emissions. The major objective of this project is to design a novel catalyst system and subject it to a series of experimentation for testing its selectivity towards alcohols. This is because the present catalytic systems are either very expensive to assemble or confer to a low yield. Two cobalt (Co) based catalysts, one without a promoter and the other which is promoted by zirconium (Zr), are prepared. The activity and selectivity of Co catalysts are finally compared with the existing Swedish Biofuels AB’s Iron (Fe) based catalyst promoted by copper (Cu) and chromium (Cr) along with characterization of the optimum reaction parameters like temperature, pressure, GHSV and syngas ratio for FTS. Aqueous incipient impregnation approach was adopted wherein the Co active metal and Zr promoter (only in second catalyst) are introduced step-wise on a ϒ-alumina support to synthesize the catalyst after which it is heat treated through drying, calcination and reduction to obtain the active Co metal catalyst. A high temperature FTS, was employed for the yield of alcohols and other gasoline derivatives according to literature. Finally, the liquid and gaseous products are analyzed through GC or GC/MS analysis techniques. The unpromoted Co catalyst’s activity is regarded as a failure due to satisfactory results. There were a few problems associated with the catalyst alone like poor mechanical stability that could be attributed to the use of an incorrect binder. Other problems included methanation due to haphazard temperature variations and inefficient catalyst reduction. For the promoted Co catalyst, the yield of alcohols and hydrocarbons was significantly higher than the unpromoted Co catalyst. A temperature of 300 °C, a GHSV of 360 h-1 , a pressure of 10 bar and a H2:CO ratio of 1.3:1 were the optimal background conditions for FTS. Higher temperature caused methanation and reduced the chain growth probability factor, α, that resulted in the formation of lower hydrocarbons only. Any increase in gas ratio and GHSV, also increased the rate of methane formation and caused diffusion limitations. For a one-stage setup with the reversal of exhaust gases, the conversion rates of CO and H2 were quite promising. This success can be attributed to a higher calcination temperature that increased the degree of reduction of Co due to formation of promoter oxides thereby enabling CO hydrogenation and H2 insertion. It helped to reduce CO2 formation as well. Even for the Fe catalyst, a low temperature, a low GHSV and low syngas ratio were preferred. But unlike its Co counterpart, a higher pressure favored an increase in yield of alcohols and other long chain hydrocarbons. Fe’s ability to support WGS reaction disturbed the molar ratio of CO and also released more CO2 that could affect the rate of syngas conversion. But, on the whole, Fe catalyst was efficient than Co catalyst for alcohol synthesis. The overall yield of alcohols was just 5% of the liquid products. Nearly 86% of the alcohol fraction comprised of C1, C2 and C3 alcohols alone and very few C4, C5 and C6 alcohols were obtained. / Denna avhandling behandlar omvandling av en blandning av H2 och CO, även kallad syngas eller producentgas, till högre eller blandade alkoholer och andra bränslen genom en process som kallas Fischer Tropsch Synthesis (FTS). Det är en bra väg som minimerar beroendet av olja och liknande fossila bränslen som bidrar till snabba klimatförändringar genom att släppa ut skadliga växthusgaser. Syngasen som används i FTS erhålls generellt genom förgasning av biomassa för att göra hela processen förnybar och för att göra det resulterande bränslet kolneutralt. Produkterna är rena på grund av föregående rengöring av syngasblandningen för att avlägsna kväveoxider, svavel och annat partikelformigt material före processen och därigenom drastiskt minska utsläppen av avgaserna. Huvudsyftet med detta projekt är att utforma ett nytt katalysatorsystem och utsätta det för en serie experiment för att testa dess selektivitet gentemot alkoholer. Detta beror på att de nuvarande katalytiska systemen antingen är mycket dyra att montera eller ge ett lågt utbyte. Två koboltbaserade (Co) -baserade katalysatorer, en utan en promotor och den andra som befordras av zirkonium (Zr), framställs. Aktiviteten och selektiviteten hos Co-katalysatorer jämförs slutligen med de befintliga Swedish Biofuels AB: s Iron (Fe) -baserade katalysator som främjas av koppar (Cu) och krom (Cr) tillsammans med karaktärisering av de optimala reaktionsparametrarna som temperatur, tryck, GHSV och syngasförhållande för FTS. Vattenhaltig begynnande impregneringsmetod användes där den Co-aktiva metallen och Zr-promotorn (endast i den andra katalysatorn) införs stegvis på ett ϒ-aluminiumoxidstöd för att syntetisera katalysatorn, varefter den värmebehandlas genom torkning, kalcering och reduktion för att erhålla aktiv Co-metallkatalysator. En hög temperatur FTS användes för utbytet av alkoholer och andra bensinderivat enligt litteratur. Slutligen analyseras de flytande och gasformiga produkterna genom GC- eller GC / MS-analystekniker. Den outpromoterade Co-katalysatorns aktivitet betraktas som ett misslyckande på grund av tillfredsställande resultat. Det fanns några problem associerade med katalysatorn ensam som dålig mekanisk stabilitet som kunde tillskrivas användningen av ett felaktigt bindemedel. Andra problem inkluderade metanering på grund av variationer i slumpmässiga temperaturer och ineffektiv katalysatorreduktion. För den befordrade Co-katalysatorn var utbytet av alkoholer och kolväten betydligt högre än den opromoterade Co-katalysatorn. En optimal temperatur på 300 ° C, en GHSV på 360 h-1, ett tryck av 10 bar och ett H2: CO-förhållande på 1,3: 1 var de optimala bakgrundsbetingelserna för FTS. Högre temperatur orsakade metanering och reducerade sannolikhetsfaktorn för kedjan tillväxt, a, vilket resulterade i bildandet av endast lägre kolväten. Varje ökning av gasförhållandet och GHSV, ökade också metanbildningshastigheten och orsakade diffusionsbegränsningar. För en inställning i ett steg med reversering av avgaser var omvandlingsgraden för CO och H2 ganska lovande. Denna framgång kan tillskrivas en högre kalcineringstemperatur som ökade graden av reduktion av Co på grund av bildning av promotoroxider och därigenom möjliggör CO-hydrering och H2-införing. Det hjälpte också till att minska koldioxidbildningen. Även för Fe-katalysatorn föredrog man en låg temperatur, ett lågt GHSV och lågt syngasförhållande. Men till skillnad från Co-motsvarigheten gynnade ett högre tryck en ökning av utbytet av alkoholer och andra långkedjiga kolväten. Fe: s förmåga att stödja WGS-reaktion störde det molära förhållandet CO och frigav också mer CO2 som kan påverka hastigheten på syngasomvandlingen. Men i stort sett var Fe-katalysator mer effektiv än Cokatalysator för alkoholsyntes. Det totala utbytet av alkoholer var bara 5% av de flytande produkterna. Nästan 86% av alkoholfraktionen bestod av C1-, C2- och C3-alkoholer enbart och mycket få C4-, C5- och C6-alkoholer erhölls.
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Contribution à l'étude mécanistique de la synthèse Fischer-Tropsch: préparation et caractérisation de catalyseurs de cobalt et de nickelBundhoo, Adam 06 September 2010 (has links)
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).<p>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.<p><p>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.<p>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.<p><p>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.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished
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Synthèse Fischer-Tropsch à partir de biosyngas dans un réacteur triphasique en utilisant des nano-carbures de fer générés par plasma comme catalyseurBlanchard, Jasmin January 2014 (has links)
La recherche sur la synthèse Fischer-Tropsch (FTS) a depuis 20 ans été fortement stimulée par la demande d’énergie croissante. Le projet de ce doctorat vise à élaborer un catalyseur nanométrique hétérogène sans porosité interne qui sera utilisé avec du gaz de synthèse produit par gazéification sous air de matières renouvelables. Les objectifs principaux consistent à valider un protocole de fabrication du catalyseur par plasma, optimiser les conditions d’opération, comparer avec une option commerciale, évaluer le potentiel des additifs et concevoir un modèle cinétique.
Le catalyseur est constitué de nanoparticules de carbure de fer encapsulées dans du carbone devant être au moins partiellement enlevé avant la réaction. Un réacteur a été conçu et les conditions optimales ont été estimées à :
• température inférieure à 250°C pour limiter la réaction de conversion du gaz à l’eau (water-gas-shift; WGS) tout en maintenant une activité optimale pour la FTS;
• pression supérieure à 15 bars pour assurer que le milieu liquide de la réaction soit saturé en réactifs, mais inférieure à 25 bars pour permettre l’évacuation de l’eau;
• une vitesse spatiale de 1 200 ml[indice inférieur gaz]/(h*g[indice inférieur cata]) qui assure une conversion maximale aux autres conditions optimisées.
Du Nanocat, un matériel commercial constitué de nanoparticules d’hématite non-supportées, a été utilisé comme matériel de référence. Il doit toutefois être transformé en carbure de fer par une réaction avec du CO. Dans le système de réaction et les conditions testées, les performances du Nanocat sont très similaires à celle du catalyseur produit par plasma. Du Cu et du K ont été utilisés comme dopants du catalyseur; le dopage est simultané à la fabrication du catalyseur. Une conversion complète et sans désactivation a été obtenue, mais l’étendue de la réaction WGS a été multipliée par 3. Ce dopage s’est avéré bénéfique mais une optimisation de la charge est requise. Le modèle choisi pour simuler la FTS est basé sur une cinétique phénoménologique : les paramètres de la réaction sont réunis en un facteur mis en fonction d’une réponse du système réactionnel. La prédiction du modèle phénoménologique est bonne pour la conversion du CO et pour la WGS, mais pas pour la conversion FTS; il donne aussi de bons résultats avec des données de la littérature.
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Fischer-Tropsch ionomeric waxesPotgieter Hennie (Hendrik Frederick) 12 1900 (has links)
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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Palladium catalysed oxidation of a-olefins to ketones.Khuzwayo, Bonakele G. January 1997 (has links)
The aim of this research project was to investigate the oxidation reactions of olefins to ketones. Initial studies revolved around the oxidation reactions of terminal olefins to symmetrical dialkyl ketones. The inability to isolate pure products, and the consumption of large amounts of the expensive palladium catalyst for each run as well as the extremely low yields that resulted from these oxidation reactions, made it difficult to thoroughly investigate this oxidation system. It was then decided to
embark on the investigation of oxidation reactions of a-olefins to methyl ketones. For these studies, six terminal olefins were oxidised to methyl ketones employing seven different oxidation reactions. One of the most important and pioneering reactions m this field is the system employing PdCl2 / CuCl2 / O2 for the oxidation of terminal olefins to methyl ketones,
namely the Wacker oxidation reaction. Experimental results, however, indicated that high product contamination from by-products resulted from these oxidation reactions despite the fairly good yields of product from the Wacker oxidation system. Some reaction systems that have been developed from the Wacker oxidation system were also investigated. The oxidation system employing PdCl2 / p-benzoquinone for the oxidation of terminal olefins to ketones was studied. The oxidation reactions
resulted in incomplete oxidation with higher olefins (l-decene, l-nonene and l-octene), and complete oxidation of lower olefins (l-heptene, l-hexene and l-pentene) under the same reaction conditions. The products from lower olefins oxidised under these reaction conditions were pure and high yielding
Another system that proved efficient both with feasibility and good yields of products was the oxidation system employing Pd(OAc)2 / H202 catalyst to oxidise terminal olefins to methyl ketones. Phase transfer catalysis has been employed in organic chemistry to effect different reactions. In this case two types of phase transfer agents were employed to effect the
oxidation of terminal olefins to ketones. The first oxidation system involved the use of a PdCl2 / CuCl2 / O2 catalyst with a quaternary ammonium salt,
cetyltrimethylammonium bromide (CTAB), to govern the course of the reaction. Reasonable yields were obtained, and moderate purity of products was also observed. The second phase transfer catalysis system employed polyethylene glycol (PEG-200) as a phase transfer agent, and PdCl2 / CuCl2 / O2 as a catalyst for oxidation of olefins to ketones. This oxidation system resulted in different isomers of a ketone from a terminal olefin. Pure methyl ketones were not isolable from the mixture of methyl and ethyl ketones. The oxidation reactions of olefins to ketones employing Pd(OAc)2 / p-benzoquinone in combination with electrolysis were also investigated. The unique feature about these reactions was the fact that cyclic olefins could also be oxidised under these conditions. Good yields were obtained, and high product purity was observed. One of the important oxidation reactions investigated during the project was the
reaction that used an alternative metal to the expensive palladium catalyst for the oxidation reactions to ketones. This oxidation system employs CuCl2 / 18-C-6 / acetaldehyde as a catalyst for the oxidation of hydrocarbons to ketones and alcohols. It was discovered during the investigation that olefins can also be used as substrates and are oxidised to the corresponding ketones. The use of olefins as substrates resulted in
higher yields than the hydrocarbon oxidation reactions, and less contamination in the product mixture was also observed. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 1997.
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Hydrogenation of carbon monoxide over modified cobalt-based catalystsColley, Saul Eric January 1991 (has links)
A thesis submitted to the Faculty of Science, University of the
Witwatersrand, Johannesburg, in fulfilment of the requirements for the
degree of Doctor of Phllosophy. / A disadvantage of the Fischer-Tropsch synthesis is that a broad
product spectrum is obtained. Economic considerations however require an
improvement in the optimization of the reaction to maximize the production
of high value commercial products, in·particular, short chain olefins and high
molecular weight hydrocarbons. [Abbreviated abstract. Open document to view full version] / AC2017
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Developing a method for process design using limited data : A Fischer-Tropsch synthesis case studyMukoma, Peter 23 October 2008 (has links)
Most of the available tools and methods applied in the design of chemical
processes are not effective at the critical early stages of design when the process
data is very limited. Businesses are often under pressure to deliver products in
shorter times and this in turn prevents the evaluation of options. Early
identification of options will allow for the development of an experimental
program that will support the design process.
The main objective of this work is to apply the Process Synthesis approach to
develop a structured method of designing a process using mostly qualitative
information based on limited experimental data, prior experience, literature and
assumptions. Fischer-Tropsch (FT) synthesis of hydrocarbons from syngas
generated by reforming natural gas and/or coal has been used as a case study to
illustrate this method. Simple calculations based on experimental data and basic
thermodynamics have been used to generate some FT Synthesis flowsheet
models. The evaluation of different flowsheet models was done using carbon
efficiency as a measure of process efficiency.
It was established that when choosing the optimal region for the operation and
design of an FT Synthesis process, the influence of the system parameters must be
well understood. This is only possible if the kinetics, reactor, and process design
are done iteratively. It was recommend not to optimize the reactor independent of
the process in which it is going to be used without understanding the impact of its
operating conditions on the entire process. Operating an FT Synthesis process at
low CO per-pass conversions was found to be more beneficial as this will avoid
the generation of high amounts of methane which normally results in large
recycles and compression costs.
Whether the process is run as a once-through or recycle process, the trend should
be to minimize the formation of lighter gases by obtaining high Alpha values because carbon efficiency increases with the increase in value. Experiments should be
performed to obtain process operating conditions that will yield high values.
However, if the aim is to maximize diesel production by hydrocracking long chain
hydrocarbons (waxes), then an optimal value should be targeted to avoid the
cost of hydrocracking these very heavy waxes. The choice of the syngas
generation technology has a direct impact on the carbon efficiency of an FT
synthesis plant. This study has established that running an FT synthesis process
with syngas obtained by steam reforming of natural gas with CO2 addition can
yield high carbon efficiencies especially in situations were CO2 is readily
available. In FT synthesis, CO2 is normally produced during energy generation
and its emission into the environment can be minimized by using it as feed during
the steam reforming of natural gas to produce syngas.
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