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La gazéification est aujourd'hui l'une des stratégies les plus prometteuses pour valoriser les déchets en énergie. Cette technologie thermo-chimique permet une réduction de 95 % de la masse des intrants et génère des cendres inertes ainsi que du gaz de synthèse (syngaz). Le syngaz est un combustible gazeux composé principalement de monoxyde de carbone (CO), d'hydrogène (H2) et de dioxyde de carbone (CO2). Le syngaz peut être utilisé pour produire de la chaleur et de l'électricité. Il est également la pierre angulaire d'un grand nombre de produits à haute valeur ajoutée, allant de l'éthanol à l'ammoniac et l'hydrogène pur. Les applications en aval de la production de syngaz sont dictées par son pouvoir calorifique, lui-même dépendant de la teneur du gaz en H2. L’augmentation du contenu du syngaz en H2 est rendu possible par la conversion catalytique à la vapeur d’eau, largement répandu dans le cadre du reformage du méthane pour la production d'hydrogène. Au cours de cette réaction, le CO est converti en H2 et CO2 selon : CO + H2O → CO2 + H2. Ce processus est possible grâce à des catalyseurs métalliques mis en contact avec le CO et de la vapeur. La conversion catalytique à la vapeur d’eau a jusqu'ici été réservé pour de grandes installations industrielles car elle nécessite un capital et des charges d’exploitations très importantes. Par conséquent, les installations de plus petite échelle et traitant des intrants de faible qualité (biomasse, déchets, boues ...), n'ont pas accès à cette technologie. Ainsi, la seule utilisation de leur syngaz à faible pouvoir calorifique, est limitée à la génération de chaleur ou, tout au plus, d'électricité. Afin de permettre à ces installations une gamme d’application plus vaste de leurs syngaz, une alternative économique à base de catalyseur biologique est proposée par l’utilisation de bactéries hyperthermophiles hydrogénogènes. L'objectif de cette thèse est d'utiliser Carboxydothermus hydrogenoformans, une bactérie thermophile carboxydotrophe hydrogénogène comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène. Pour cela, l’impact d'un phénomène de biominéralisation sur la production d’H2 a été étudié. Ensuite, la faisabilité et les limites de l’utilisation de la souche dans un bioréacteur ont été évaluées. Tout d'abord, la caractérisation de la phase inorganique prédominante lorsque C. hydrogenoformans est inoculé dans le milieu DSMZ, a révélé une biominéralisation de phosphate de calcium (CaP) cristallin en deux phases. L’analyse par diffraction des rayons X et spectrométrie infrarouge à transformée de Fourier de ce matériau biphasique indique une signature caractéristique de la Mg-whitlockite, alors que les images obtenues par microscopie électronique à transmission ont montré l'existence de nanotiges cristallines s’apparentant à de l’hydroxyapatite. Dans les deux cas, le mode de biominéralisation semble être biologiquement induit plutôt que contrôlé. L'impact du précipité de CaP endogène sur le transfert de masse du CO et la production d’H2 a ensuite été étudié. Les résultats ont été comparés aux valeurs obtenues dans un milieu où aucune précipitation n'est observée. Dans le milieu DSMZ, le KLa apparent (0.22 ± 0.005 min-1) et le rendement de production d’H2 (89.11 ± 6.69 %) étaient plus élevés que ceux obtenus avec le milieu modifié (0.19 ± 0.015 min-1 et 82.60 ± 3.62% respectivement). La présence du précipité n'a eu aucune incidence sur l'activité microbienne. En somme, le précipité de CaP offre une nouvelle stratégie pour améliorer les performances de transfert de masse du CO en utilisant les propriétés hydrophobes de gaz. En second lieu, la conversion du CO en H2 par la souche Carboxydothermus hydrogenoformans fut étudiée et optimisée dans un réacteur gazosiphon de 35 L. Parmi toutes les conditions opérationnelles, le paramètre majeur fut le ratio du débit de recirculation du gaz sur le débit d'alimentation en CO (QR:Qin). Ce ratio impacte à la fois l'activité biologique et le taux de transfert de masse gaz-liquide. En effet, au dessus d’un ratio de 40, les performances de conversion du CO en H2 sont limitées par l’activité biologique alors qu’en dessous, elles sont limitées par le transfert de masse. Cela se concrétise par une efficacité de conversion maximale de 90.4 ± 0.3 % et une activité spécifique de 2.7 ± 0.4 molCO·g–1VSS·d–1. Malgré des résultats prometteurs, les performances du bioréacteur ont été limitées par une faible densité cellulaire, typique de la croissance planctonique de C. hydrogenoformans. Cette limite est le facteur le plus contraignant pour des taux de charge de CO plus élevés. Ces performances ont été comparées à celles obtenues dans un réacteur à fibres creuses (BRFC) inoculé par la souche. En dépit d’une densité cellulaire et d’une activité volumétrique plus élevées, les performances du BRFC à tout le moins cinétiquement limitées quand elles n’étaient pas impactées par le transfert de masse, l'encrassement et le vieillissement de la membrane. Afin de parer à la dégénérescence de C. hydrogenoformans en cas de pénurie de CO, la croissance de la bactérie sur pyruvate en tant que seule source de carbone a été également caractérisée. Fait intéressant, en présence simultanée de pyruvate et de CO, C. hydrogenoformans n’a amorcé la consommation de pyruvate qu’une fois le CO épuisé. Cela a été attribué à un mécanisme d'inhibition du métabolisme du pyruvate par le CO, faisant ainsi du pyruvate le candidat idéal pour un système in situ de secours. / Gasification is today one of the most promising strategies to recover energy from waste. This thermo-chemical technology allows a 95% weight reduction of the input and generates inorganic inert ashes as well as a synthesis gas (syngas). Syngas is a gaseous fuel mainly composed of carbon monoxide (CO), hydrogen (H2) and carbon dioxide (CO2). Syngas can be burned to produce heat and electricity. It is also the building block of many high added- value products ranging from ethanol to ammonia and pure hydrogen. Downstream applications of syngas production will depend on its heating value, which is determined by its content in H2. Upgrading the H2 content in syngas is performed by the water-gas shift (WGS) reaction, widely utilized during methane reforming for hydrogen production. During the WGS reaction CO is converted to H2 and CO2 according to: CO + H2O → CO2 + H2. This process is achieved using a metallic catalyst in a heterogeneous gas-phase reaction with CO and steam. The WGS reaction has so far been reserved for large-scale gasification plants and requires high capital and operational expenditures. Hence, smaller scale plants that process low-grade materials (biomass, waste, sludge...), would not have access to such technology. The only possible outcome with the synthesis gas (syngas) produced and which generally has a poor heating value, is to generate heat or at best, electricity. In order to offer small plants access to the WGS reaction and to a higher range of products from their syngas, an alternative to the expensive and energy-intensive established catalyst-based WGS is here considered, such as extreme-thermophilic microbial processes carried out by hydrogenogens. The goal of this thesis was to use Carboxydothermus hydrogenoformans, a thermophilic carboxydotrophic hydrogenogenic bacterium as a biological catalyst for the WGS reaction. This was done by characterizing the impact of a growth-associated biomineralization phenomenon on H2 production and assessing the feasibility and limitations of using the strain in a bioreactor. First, characterization of the predominant inorganic phase when Carboxydothermus hydrogenoformans was inoculated in the DSMZ medium revealed the biomineralization of two crystalline CaP phases. The X-ray diffractometry peaks and Fourier transform infrared spectroscopy spectrum of this biphasic material consistently showed features characteristic of Mg-whitlockite, whereas transmission electron microscopy analysis showed the existence of hydroxyapatite-like nanorods crystals. In both cases, the mode of biomineralization appears to be biologically induced rather than biologically controlled. The impact of the endogenous CaP precipitate on CO mass transfer and H2 production was thus assessed and compared to a medium where no precipitation was observed. In the DSMZ medium, the apparent KLa (0.22 ±0.005 min-1) and H2 production yield (89.11 ±6.69%) were higher than the ones obtained in the modified medium (0.19 ±0.015 min-1 and 82.60 ±3.62% respectively). The presence of the precipitate had no impact on C. hydrogenoformans CO uptake. Overall, the CaP precipitate offers a novel strategy for gas-liquid mass transfer enhancement using CO hydrophobic properties. Second, the conversion of CO into H2 by C. hydrogenoformans was investigated and optimized in a 35 L gas-lift reactor. Upon all operational conditions, the ratio of gas recirculation over CO feed flow rates (QR:Qin) was the major parameter that impacted both biological activity and volumetric gas-liquid mass transfer. The CO conversion performance of the gas lift reactor was kinetically limited over a QR:Qin ratio of 40, and mass transfer limited below that ratio, resulting in a maximum conversion efficiency of 90.4±0.3% and a biological activity of 2.7±0.4 molCO· g–1VSS· day–1. Despite very promising results, CO conversion performance was limited by a low cell density, typical of C. hydrogenoformans planktonic growth. This limitation was found to be the most restrictive factor for higher CO loading rates. Results were compared to the performance of the strain inoculated in a hollow fiber membrane bioreactor where performance, despite the higher cell density and volumetric activity, was biokinetically limited, when not limited by gas–liquid mass transfer, membrane fouling and aging. To avoid any C. hydrogenoformans decay during potential CO shortages, growth of the bacterium on pyruvate as a sole carbon source was characterized. Interestingly, when grown simultaneously on pyruvate and CO, pyruvate consumption was initiated upon CO depletion. This was attributed to the inhibition of pyruvate oxidation by CO, making pyruvate the ideal candidate for an in-situ back-up system.

A goal of the Swedish government is to increase the usage of renewable fuels and biomass-based fuels. Fuel cells, and especially the MCFC, are useful for these types of fuels. The Swedish market may benefit from the MCFC in two ways: increased efficiency of the biofuels and also utilisation of produced heat in district heating. Most of the commercial MCFC systems today are optimised for use with methane. The possibility to utilise biomass in Sweden makes it important to study how the MCFC may be adapted or optimised for good performance and low degradation with gas produced from biomass or other renewable fuels. This thesis is focused on methods that may be used to investigate and evaluate MCFC electrodes and electrolytes with renewable fuels i.e. CO2-containing gases. The methods and results are both experimental and mathematically modelled. The objectives of this thesis are to better understand how the performance of the anode is dependent on different fuels. Anode kinetics and the water-gas shift reaction have been investigated as well as the possibility to increase cell lifetime by increasing the initial electrolyte amount by having the anode as a reservoir. The effect of segregation of cations in the electrolyte during operation has also been studied. It was found that if the gas composition at the current collector inlet is in equilibrium according to the water gas-shift reaction the gas composition inside the electrode is almost uniform. However, if the gas is not in equilibrium then the concentration gradients inside the current collector have a large effect on the gas composition inside the electrode. The conversion of the gas in the gas flow channels according to the water-gas shift reaction depends on the gas flow rate. For an anode used in a gas mixture of humidified hydrogen and carbon dioxide that are not in equilibrium some solubility of Ni in a (Li/Na)2CO3 mixture was found. To have the anode act as an electrolyte reservoir to prolong cell lifetime the anode pore size should be carefully matched with that of the cathode and a bimodal pore-size distribution for the anode is preferable to have as good performance as possible for as large electrolyte filling degree interval as possible. Modelling results of segregation of cations in the electrolyte during operation indicate that the electrolyte composition changes during operation and that the lithium ions are enriched at the anode for both types of electrolyte used for the MCFC. The electrolyte composition changes are small but might have to be considered in long-time operation. The results from this thesis may be used to better understand how the MCFC may be used for operation with renewable fuels and how electrodes may be designed to prolong cell lifetime. / Ett av den svenska regeringens mål är att öka användandet av förnyelsebara bränslen och bränslen från biomassa. Bränsleceller och framförallt MCFC är användbara för dessa typer av bränslen. Den svenska marknaden kan dra fördelar av MCFC på två sätt; ökad bränsleutnyttjandegrad och utnyttjande av producerad värme för fjärrvärme. De flesta kommersiella MCFC-systemen idag är optimerade för användning av metan. Möjligheten att använda biomassa på den svenska marknaden gör det viktigt att studera hur MCFC kan anpassas eller optimeras för bra prestanda och låg degradering för användning med gas från biomassa eller andra förnyelsebara bränslen. Fokus i denna avhandling är på metoder som kan användas för att undersöka och utvärdera MCFC-elektroder och -elektrolyter med förnyelsebara bränslen, dvs. gaser innehållande CO2. Metoderna och resultaten är både experimentella och matematiskt modellerade. Målet med denna avhandling är att bättre förstå hur anodens prestanda beror på användningen av olika bränslen. Anodens kinetik och vattengasskiftreaktionen har studerats liksom möjligheten att förlänga cellens livstid genom att öka den initiala mängden elektrolyt medelst användning av anoden som reservoar. Effekten av segregation av katjoner i elektrolyten under last har också undersökts. Om gassammansättningen är i jämvikt enligt vattengasskiftreaktionen vid inloppet till strömtilledaren kommer gassammansättningen att vara nära uniform inuti elektroden. Om ingående gas inte är i jämvikt kommer stora koncentrationsgradienter uppkomma i strömtilledaren och påverka gassammansättningen i elektroden. Omsättningen med avseende på vattenskiftreaktionen av gasen i flödeskanalen verkar vara beroende av gasens flödeshastighet. För en anod som används i en uppfuktad blandning av vätgas och koldioxid som inte är i jämvikt befanns det att Ni har en viss löslighet i (Li/Na)2CO3. För att kunna använda anoden som reservoar för elektrolyt för att förlänga livstiden för MCFC skall anodens porstorleksfördelning överensstämma med katodens och ha en bimodal porstorleksfördelning för att ge en tillräckligt god prestanda i ett så stort elektrolytfyllnadsgradsintervall som möjligt. Modelleringsresultat för segregering av katjoner i elektrolyten under drift visar att litiumjoner anrikas i anoden för båda typerna av elektrolyt som används i MCFC. Elektrolytkoncentrationsförändringarna är små men kan behövas tas i beaktande vid långa driftstider. Denna avhandlings resultat kan användas för att bättre förstå hur MCFC skall anpassas för drift med förnyelsebara bränslen och hur elektroder kan utformas för att förlänga livstiden. / QC 20100630

Among the various heterogeneous catalytic reactions three way catalysis (TWC), catalytic combustion of hydrogen, water gas shift reaction (WGS) and preferential oxidation of CO (PROX) in the hydrogen rich stream are some of the important reactions receiving the attention presently. Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) from the automobile exhaust. Catalytic combustion of hydrogen by oxygen or hydrogen-oxygen recombination reaction is an industrially important reaction. It has variety of application such as in sealed lead acid batteries and nuclear reactors. Water gas shift (WGS) reaction is of specific importance to produce hydrogen from carbonaceous material. PROX is an important step to further purify hydrogen produced form WGS. Hydrogen purified using PROX can be directly fed to polymer electrolyte membrane fuel cells. By and large, noble metals Pt, Pd, Rh, Ru and some of their alloys are dispersed on oxide or high surface area carbon are the active catalysts. An alternative approach can be to make Pt2+, Pd2+, Rh3+, Ru4+ ions substituted in reducible support such as CeO2, Ce1-xTixO2-δ and TiO2 to increase the dispersion and bring down the cost. In this thesis we have followed this new approach and show that noble metal ionic catalysts are superior to noble metal nano particles. In the 1st chapter we present an overview of heterogeneous catalysis and important heterogeneous catalytic reactions. Monolithic catalyst and various ways to coat catalysts for application have been reviewed. Metal-support interaction till date is also reviewed. In the 2nd chapter, synthesis of noble metal ionic catalysts by solution combustion method is described. Coating of washcoat and active catalyst phase over ceramic honeycomb by a new combustion method is described. Solution combustion reaction and characterization of the catalyst by x-ray diffraction, x-ray photoelectron spectroscopy, temperature programmed reduction and reaction is given. We have fabricated experimental systems to carryout catalytic reaction and in this chapter they have been presented. In the 3rd chapter, we report a new process of coating of active exhaust catalyst over -Al2O3 coated cordierite honeycomb. The process consists of (a) growing  -Al2O3 on cordierite by solution combustion of Al(NO3)3 and oxylyldihydrazide (ODH) at 600 0C. Active catalyst phase, Ce0.98Pd0.02O2- is coated on - Al2O3 coated cordierite again by combustion of ceric ammonium nitrate and ODH with 1.2  10-3 M PdCl2 solution at 500 0C. In this way a coat layer over cordierite ceramic has been achieved and catalyst has the active sites in the form of Pd2+ ions rather than Pd metal. Weight of the active catalyst can be varied from 0.02 to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion [1]. Adhesion of catalyst to cordierite surface is via oxide growth on oxide ceramic which is very strong. 100 % conversion of CO is achieved below 80 oC at a space velocity of 880 h-1. At much higher space velocity of 21000h-1, 100 % conversion is obtained below 245 oC. Activation energy for CO oxidation is 8.4 kcal/mol. At a space velocity of 880 h-1 100% NO conversion is attained below 185 oC and 100 % conversion of ‘HC’(C2H2) below 220 oC. At the same space velocity 3-way catalytic performance over Ce0.98Pd0.02O2- coated monolith shows 100% conversion of all the pollutants below 220 o C with 15% excess oxygen. Catalytic activity of cordierite honeycomb coated by this new coating method for the oxidation of major hydrocarbons in exhaust gas is discussed further in this chapter. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. 3-way catalytic test is done by putting hydrocarbon mixture along with CO (10000ppm), NO (2000ppm) and O2 (15000ppm). Below 350 oC full conversion is achieved [2]. A comparison of the results shows that Ce1-xPdxO2-δ far superior to other catalysts. In this method, handling of nano material powder is avoided. In the 4th chapter we present a detailed study on the catalytic combustion of hydrogen by oxygen (hydrogen oxygen recombination reaction). Ever since Michel Faraday showed H2 + O2 recombination reaction over platinum metal plates, Pt metal has remained the only room temperature recombination catalyst. In search of an alternative catalyst, we discovered a new Pt free Ti0.99Pd0.01O2- compound which shows high rates of this reaction above 45 oC compared to Ce0.98Pt0.02O2-, Pt/Al2O3 and Pd/Al2O3. High rates of H2+O2 recombination over Pt and Pd ion respectively in CeO2 and TiO2 is due to the protonic type H2+ adsorption on Pt2+ or Pd2+ and dissociative chemisorption of O2 on the electron rich oxide ion vacancies [3]. In the case of Ce0.98Pt0.02O2-, H2/Pt ratio in a TPR experiment is ~2.3 at 0 oC. In the case of Ti0.99Pd0.01O2- also, H2 adsorption occurs below 0 oC and H2 / Pd ratio is ~2.2. Thus, more than 4-5 H atoms are adsorbed per metal ion. This is attributed to hydrogen spillover. H2 is known to be adsorbed as hydride ion (H-) over Pt, Pd, Rh, Ru, Os and Ir metals. Proton NMR studies of H2 adsorbed on Pd metal have shown upfield i.e. negative shift of 12 ppm with respect to TMS. We have studied proton NMR of Ti0.99Pd0.01O2- + H2 which show a downfield shift of 11.35 ppm confirming H+ or H2+ kind of species over Pd2+ ion in Ti0.99Pd0.01O2-. In Ce0.98Pt0.02O2- also H2 adsorption led to H2+ like species observed at 8 ppm and DFT calculations indeed showed H2+ kind species. H2+ is a precursor for dissociation and can readily induce O2 dissociation leading to high rates of recombination. In the 5th chapter we report water gas shift reaction (WGS) and preferential oxidation of CO (PROX) over Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ. The water gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nano crystalline catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2 and Ce1-xTixO2-δ. The catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS) and it has been shown that Pt2+ ions in these reducible oxides of the form Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ are highly active. These catalysts were tested for the water gas shift reaction both in presence and absence of hydrogen. It is shown that Ti0.99Pt0.01O2- exhibits higher catalytic activity than Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ [4]. Further, experiments were conducted to determine the deactivation of these catalysts by performing the daily startup and shutdown of the reactor for over 24 hours. There was no sintering of Pt and no carbonate formation and, therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ce4+, Ti4+ ions in the catalysts. Further, PROX activity of these catalysts has been studied. Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ showed high activity, large operating temperature window and low working temperature proving them to be highly effective PROX catalysts. In the 6th chapter we study the electrocatalysis of formic acid electro-oxidation and simultaneously mapping the electronic states of the electrodes by X-ray photoelectron spectroscopy (XPS). Ionically dispersed platinum in Ce1-xPtxO2-δ and Ce1-x-yTiyPtxO2-δ is very active towards oxygen evolution and formic acid oxidation. Higher electro-catalytic activity of Pt2+ ions in CeO2 and Ce1-xTixO2 compared to Pt0 in Pt/C is due to Pt2+ ion interaction with the supports, CeO2 and Ce1-xTixO2 respectively [5]. Further, ionic platinum does not suffer from CO poisoning effect unlike Pt0 in Pt/C. Utilization of lattice oxygen from the electrodes during the reaction has been demonstrated. This lattice oxygen exchange is responsible to convert CO to CO2 in the lower potential region to remove CO poisoning effect. In 7th chapter we repeat our study on the noble metal ion reducible oxide interaction in Ce1-xPtxO2- and Ce1-xPdxO2- (x= 0.02) system by a novel electrochemical method combined with XPS. Working electrodes made of CeO2 and Ce0.98Pt0.02O2- mixed with 30% carbon are cycled between 0.0-1.2 V in potentio-static (chronoamperometry) and potentio-dynamic (cyclic voltametry) mode with reference to saturated calomel electrode (SCE). Reversible oxidation of Pt0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y= 0.35) after applying +1.2 V which is not reversible. But Ce0.98Pt0.02O2- reaches a steady state with Pt2+: Pt4+ in the ratio of 0.60: 0.40 and Ce4+: Ce3+ in the ratio of 0.55: 0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V which is reversible [6]. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2- forms a stable electrode for oxidation of H2O to O2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction of Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple. Similar studies have been performed with Ce0.98Pd0.02O2- catalyst to show the redox coupling between Pd2+/Pd0 and Ce4+/Ce3+ redox couples. We expect similar redox coupling for Pd, Pt ions substituted TiO2, and Ce1-xTixO2. In the final chapter 8, a critical review and conclusion on the results presented in the thesis is presented. The combustion synthesized catalysts reported in this thesis stabilizes the Pt and Pd metals in their ionic state rather than zero valent metallic state. Thus, the catalysts are uniform solid catalysts. High activity and stability of these catalysts are shown to be due to the electronic interaction between noble metal ions and the reducible oxide. Redox couples Pt0/Pt2+, Pt2+/Pt4+ and Pd0/Pd2+ interact with Ce4+/Ce3+, Ti4+/Ti3+ couples such that metal is oxidized and the support is reduced. This has been established in the thesis by a combined use of electrochemistry and XPS thus solving a long standing problem of metal support interaction in catalysis. We hope that the results presented in the thesis is a worthwhile contribution to catalysis. (For mathematical equations pl refer pdf file.)

La gazéification est aujourd'hui l'une des stratégies les plus prometteuses pour valoriser les déchets en énergie. Cette technologie thermo-chimique permet une réduction de 95 % de la masse des intrants et génère des cendres inertes ainsi que du gaz de synthèse (syngaz). Le syngaz est un combustible gazeux composé principalement de monoxyde de carbone (CO), d'hydrogène (H2) et de dioxyde de carbone (CO2). Le syngaz peut être utilisé pour produire de la chaleur et de l'électricité. Il est également la pierre angulaire d'un grand nombre de produits à haute valeur ajoutée, allant de l'éthanol à l'ammoniac et l'hydrogène pur. Les applications en aval de la production de syngaz sont dictées par son pouvoir calorifique, lui-même dépendant de la teneur du gaz en H2. L’augmentation du contenu du syngaz en H2 est rendu possible par la conversion catalytique à la vapeur d’eau, largement répandu dans le cadre du reformage du méthane pour la production d'hydrogène. Au cours de cette réaction, le CO est converti en H2 et CO2 selon : CO + H2O → CO2 + H2. Ce processus est possible grâce à des catalyseurs métalliques mis en contact avec le CO et de la vapeur. La conversion catalytique à la vapeur d’eau a jusqu'ici été réservé pour de grandes installations industrielles car elle nécessite un capital et des charges d’exploitations très importantes. Par conséquent, les installations de plus petite échelle et traitant des intrants de faible qualité (biomasse, déchets, boues ...), n'ont pas accès à cette technologie. Ainsi, la seule utilisation de leur syngaz à faible pouvoir calorifique, est limitée à la génération de chaleur ou, tout au plus, d'électricité. Afin de permettre à ces installations une gamme d’application plus vaste de leurs syngaz, une alternative économique à base de catalyseur biologique est proposée par l’utilisation de bactéries hyperthermophiles hydrogénogènes. L'objectif de cette thèse est d'utiliser Carboxydothermus hydrogenoformans, une bactérie thermophile carboxydotrophe hydrogénogène comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène. Pour cela, l’impact d'un phénomène de biominéralisation sur la production d’H2 a été étudié. Ensuite, la faisabilité et les limites de l’utilisation de la souche dans un bioréacteur ont été évaluées. Tout d'abord, la caractérisation de la phase inorganique prédominante lorsque C. hydrogenoformans est inoculé dans le milieu DSMZ, a révélé une biominéralisation de phosphate de calcium (CaP) cristallin en deux phases. L’analyse par diffraction des rayons X et spectrométrie infrarouge à transformée de Fourier de ce matériau biphasique indique une signature caractéristique de la Mg-whitlockite, alors que les images obtenues par microscopie électronique à transmission ont montré l'existence de nanotiges cristallines s’apparentant à de l’hydroxyapatite. Dans les deux cas, le mode de biominéralisation semble être biologiquement induit plutôt que contrôlé. L'impact du précipité de CaP endogène sur le transfert de masse du CO et la production d’H2 a ensuite été étudié. Les résultats ont été comparés aux valeurs obtenues dans un milieu où aucune précipitation n'est observée. Dans le milieu DSMZ, le KLa apparent (0.22 ± 0.005 min-1) et le rendement de production d’H2 (89.11 ± 6.69 %) étaient plus élevés que ceux obtenus avec le milieu modifié (0.19 ± 0.015 min-1 et 82.60 ± 3.62% respectivement). La présence du précipité n'a eu aucune incidence sur l'activité microbienne. En somme, le précipité de CaP offre une nouvelle stratégie pour améliorer les performances de transfert de masse du CO en utilisant les propriétés hydrophobes de gaz. En second lieu, la conversion du CO en H2 par la souche Carboxydothermus hydrogenoformans fut étudiée et optimisée dans un réacteur gazosiphon de 35 L. Parmi toutes les conditions opérationnelles, le paramètre majeur fut le ratio du débit de recirculation du gaz sur le débit d'alimentation en CO (QR:Qin). Ce ratio impacte à la fois l'activité biologique et le taux de transfert de masse gaz-liquide. En effet, au dessus d’un ratio de 40, les performances de conversion du CO en H2 sont limitées par l’activité biologique alors qu’en dessous, elles sont limitées par le transfert de masse. Cela se concrétise par une efficacité de conversion maximale de 90.4 ± 0.3 % et une activité spécifique de 2.7 ± 0.4 molCO·g–1VSS·d–1. Malgré des résultats prometteurs, les performances du bioréacteur ont été limitées par une faible densité cellulaire, typique de la croissance planctonique de C. hydrogenoformans. Cette limite est le facteur le plus contraignant pour des taux de charge de CO plus élevés. Ces performances ont été comparées à celles obtenues dans un réacteur à fibres creuses (BRFC) inoculé par la souche. En dépit d’une densité cellulaire et d’une activité volumétrique plus élevées, les performances du BRFC à tout le moins cinétiquement limitées quand elles n’étaient pas impactées par le transfert de masse, l'encrassement et le vieillissement de la membrane. Afin de parer à la dégénérescence de C. hydrogenoformans en cas de pénurie de CO, la croissance de la bactérie sur pyruvate en tant que seule source de carbone a été également caractérisée. Fait intéressant, en présence simultanée de pyruvate et de CO, C. hydrogenoformans n’a amorcé la consommation de pyruvate qu’une fois le CO épuisé. Cela a été attribué à un mécanisme d'inhibition du métabolisme du pyruvate par le CO, faisant ainsi du pyruvate le candidat idéal pour un système in situ de secours. / Gasification is today one of the most promising strategies to recover energy from waste. This thermo-chemical technology allows a 95% weight reduction of the input and generates inorganic inert ashes as well as a synthesis gas (syngas). Syngas is a gaseous fuel mainly composed of carbon monoxide (CO), hydrogen (H2) and carbon dioxide (CO2). Syngas can be burned to produce heat and electricity. It is also the building block of many high added- value products ranging from ethanol to ammonia and pure hydrogen. Downstream applications of syngas production will depend on its heating value, which is determined by its content in H2. Upgrading the H2 content in syngas is performed by the water-gas shift (WGS) reaction, widely utilized during methane reforming for hydrogen production. During the WGS reaction CO is converted to H2 and CO2 according to: CO + H2O → CO2 + H2. This process is achieved using a metallic catalyst in a heterogeneous gas-phase reaction with CO and steam. The WGS reaction has so far been reserved for large-scale gasification plants and requires high capital and operational expenditures. Hence, smaller scale plants that process low-grade materials (biomass, waste, sludge...), would not have access to such technology. The only possible outcome with the synthesis gas (syngas) produced and which generally has a poor heating value, is to generate heat or at best, electricity. In order to offer small plants access to the WGS reaction and to a higher range of products from their syngas, an alternative to the expensive and energy-intensive established catalyst-based WGS is here considered, such as extreme-thermophilic microbial processes carried out by hydrogenogens. The goal of this thesis was to use Carboxydothermus hydrogenoformans, a thermophilic carboxydotrophic hydrogenogenic bacterium as a biological catalyst for the WGS reaction. This was done by characterizing the impact of a growth-associated biomineralization phenomenon on H2 production and assessing the feasibility and limitations of using the strain in a bioreactor. First, characterization of the predominant inorganic phase when Carboxydothermus hydrogenoformans was inoculated in the DSMZ medium revealed the biomineralization of two crystalline CaP phases. The X-ray diffractometry peaks and Fourier transform infrared spectroscopy spectrum of this biphasic material consistently showed features characteristic of Mg-whitlockite, whereas transmission electron microscopy analysis showed the existence of hydroxyapatite-like nanorods crystals. In both cases, the mode of biomineralization appears to be biologically induced rather than biologically controlled. The impact of the endogenous CaP precipitate on CO mass transfer and H2 production was thus assessed and compared to a medium where no precipitation was observed. In the DSMZ medium, the apparent KLa (0.22 ±0.005 min-1) and H2 production yield (89.11 ±6.69%) were higher than the ones obtained in the modified medium (0.19 ±0.015 min-1 and 82.60 ±3.62% respectively). The presence of the precipitate had no impact on C. hydrogenoformans CO uptake. Overall, the CaP precipitate offers a novel strategy for gas-liquid mass transfer enhancement using CO hydrophobic properties. Second, the conversion of CO into H2 by C. hydrogenoformans was investigated and optimized in a 35 L gas-lift reactor. Upon all operational conditions, the ratio of gas recirculation over CO feed flow rates (QR:Qin) was the major parameter that impacted both biological activity and volumetric gas-liquid mass transfer. The CO conversion performance of the gas lift reactor was kinetically limited over a QR:Qin ratio of 40, and mass transfer limited below that ratio, resulting in a maximum conversion efficiency of 90.4±0.3% and a biological activity of 2.7±0.4 molCO· g–1VSS· day–1. Despite very promising results, CO conversion performance was limited by a low cell density, typical of C. hydrogenoformans planktonic growth. This limitation was found to be the most restrictive factor for higher CO loading rates. Results were compared to the performance of the strain inoculated in a hollow fiber membrane bioreactor where performance, despite the higher cell density and volumetric activity, was biokinetically limited, when not limited by gas–liquid mass transfer, membrane fouling and aging. To avoid any C. hydrogenoformans decay during potential CO shortages, growth of the bacterium on pyruvate as a sole carbon source was characterized. Interestingly, when grown simultaneously on pyruvate and CO, pyruvate consumption was initiated upon CO depletion. This was attributed to the inhibition of pyruvate oxidation by CO, making pyruvate the ideal candidate for an in-situ back-up system.

Abstract The energy consumption around the globe is on the rise due to the exponential population growth and urbanization. There is a need for alternative and non-conventional energy sources, which are CO2-neutral, and a need to produce less or no environmental pollutants and to have high energy efficiency. One of the alternative approaches is hydrogen economy with the fuel cell (FC) technology which is forecasted to lead to a sustainable society. Hydrogen (H2) is recognized as a potential fuel and clean energy carrier being at the same time a carbon-free element. Moreover, H2 is utilized in many processes in chemical, food, metallurgical, and pharmaceutical industry and it is also a valuable chemical in many reactions (e.g. refineries). Non-renewable resources have been the major feedstock for H2 production for many years. At present, ~50% of H2 is produced via catalytic steam reforming of natural gas followed by various down-stream purification steps to produce ~99.99% H2, the process being highly energy intensive. Henceforth, bio-fuels like biomass derived alcohols (e.g. bio-ethanol and bio-glycerol), can be viable raw materials for the H2 production. In a membrane based reactor, the reaction and selective separation of H2 occur simultaneously in one unit, thus improving the overall reactor efficiency. The main motivation of this work is to produce H2 more efficiently and in an environmentally friendly way from bio-alcohols with a high H2 selectivity, purity and yield. In this thesis, the work was divided into two research areas, the first being the catalytic studies using metal decorated carbon nanotube (CNT) based catalysts in steam reforming of ethanol (SRE) at low temperatures (<450 °C). The second part was the study of steam reforming (SR) and the water-gas-shift (WGS) reactions in a membrane reactor (MR) using dense and composite Pd-based membranes to produce high purity H2. CNTs were found to be promising support materials for the low temperature reforming compared to conventional catalyst supports, e.g. Al2O3. The metal/metal oxide decorated CNTs presented active particles with narrow size distribution and small size (~2–5 nm). The ZnO promoted Ni/CNT based catalysts showed the highest H2 selectivity of ~76% with very low CO selectivity <1%. Ethanol was shown to be a more suitable and viable source for H2 than glycerol. The dense Pd-Ag membrane had higher selectivity but a lower permeating flux than the composite membrane. The MR performance is also dependent on the active catalyst materials and thus, both the catalyst and membrane play an important role. Overall, the membrane–assisted reformer outperforms the conventional reformer and it is a potential technology in pure H2 production. The high purity of H2 gas with a CO-free reformate for fuel cell applications can be gained using the MR system. / Tiivistelmä Maailman energiankulutus on kasvussa räjähdysmäisen väestönkasvun ja voimakkaan kaupungistumisen myötä. Tällä hetkellä energian tuottamisen aiheuttamat ympäristöongelmat ja taloudellinen epävarmuus ovat seikkoja, joiden ratkaisemiseksi tarvitaan vaihtoehtoisia ja ei-perinteisiä energialähteitä, joilla on korkea energiasisältö ja jotka tuottavat vähän hiilidioksidipäästöjä. Eräs vaihtoehtoisista lähestymistavoista on vetytalous yhdistettynä polttokennotekniikkaan, minkä on esitetty helpottavan siirtymistä kestävään yhteiskuntaan. Vety on puhdas ja hiilivapaa polttoaine ja energian kantaja. Lisäksi vetyä käytetään monissa prosesseissa kemian-, elintarvike-, metalli- ja lääketeollisuudessa ja se on arvokas kemikaali monissa prosesseissa (mm. öljynjalostamoissa). Uusiutumattomat luonnonvarat ovat olleet tähän saakka merkittävin vedyn tuotannon raaka-aine. Tällä hetkellä noin 50 % vedystä tuotetaan maakaasun katalyyttisellä höyryreformoinilla. Puhtaan (yli 99,99 %) vedyn tuotanto vaatii kuitenkin useita puhdistusvaiheita, jotka ovat erittäin energiaintensiivisiä. Integroimalla reaktio- ja puhdistusvaihe samaan yksikköön (membraanireaktori) saavutetaan huomattavia kustannussäästöjä. Biopolttoaineet, kuten biomassapohjaiset alkoholit (bioetanoli ja bioglyseroli), ovat vaihtoehtoisia lähtöaineita vedyn valmistuksessa. Tämän työn tavoitteena on tuottaa vetyä bioalkoholeista tehokkaasti (korkea selektiivisyys ja saanto) ja ympäristöystävällisesti. Tutkimus on jaettu kahteen osaan, joista ensimmäisessä tutkittiin etanolin katalyyttistä höyryreformointia matalissa lämpötiloissa (<450 °C) hyödyntämällä metallipinnoitettuja hiilinanoputkia. Työn toisessa osassa höyryreformointia ja vesikaasun siirtoreaktioa tutkittiin membraanireaktorissa käyttämällä vedyn tuotantoon tiheitä palladiumpohjaisia kalvoja sekä huokoisia palladiumkomposiittikalvoja. Hiilinanoputket (CNT) havaittiin lupaaviksi katalyyttien tukimateriaaleiksi verrattuna tavanomaisesti valmistettuihin tukiaineisiin, kuten Al2O3. CNT-tukiaineelle pinnoitetuilla aktiivisilla aineilla (metalli-/metallioksidit) todettiin olevan pieni partikkelikoko (~2–5 nm) ja kapea partikkelikokojakauma. Sinkkioksidin (ZnO) lisäyksellä Ni/CNT-katalyytteihin saavutettiin korkea vetyselektiivisyys (~76 %) ja erittäin alhainen hiilimoksidiselektiivisyys (<1 %). Etanolin todettiin olevan parempi vedyn raaka-aine kuin glyserolin. Tiheillä Pd-Ag-kalvoilla havaittiin olevan vedyn suhteen korkeampi selektiivisyys mutta matalampi vuo verrattuna palladiumkomposiittikalvoihin. Membraanireaktorin suorituskyky oli riippuvainen myös katalyytin aktiivisuudesta, joten sekä kalvolla että katalyyttimateriaalilla oli merkittävä rooli kyseisessä reaktorirakenteessa. Yhteenvetona voidaan todeta, että membraanierotukseen perustuva reformointiyksikkö on huomattavasti perinteistä reformeriyksikköä suorituskykyisempi mahdollistaen tehokkaan teknologian puhtaan vedyn tuottamiseksi. Membraanitekniikalla tuotettua puhdasta vetyä voidaan hyödyntää mm. polttokennojen polttoaineena.

As the need for both sustainable energy production and waste minimization increases, the gasification of biomass becomes an increasingly important process. What would otherwise be considered waste can now be used as fuel, and the benefits of volume reduction through gasification are seen in the increased lifespan of landfills. Fluidized-bed gasification is a particularly robust technology, and allows for the conversion of most types of waste biomass. Within a fluidized-bed gasifier, thermal medium (sand) is heated to operating temperature (around 1350°F) and begins to fluidize due to the rapid expansion of air entering the bottom of the reactor. This fluidization allows for excellent heat transfer and contact between gases and solids, and prevents localized "hot spots" within the gasifier, thereby reducing the occurrence of ash agglomeration within the gasifier. Solids enter the middle of the gasifier and are rapidly dried and devolatilized, and the products of this step are subsequently oxidized and then reduced in the remainder of the gasifier. A syngas composed mainly of N2, H2O, CO2, CO, CH4, and H2 exits the top of the gasifier. A computer model was developed to predict the syngas composition and flow rate, as well as ash composition and mass flow rate from a fluidized-bed gasifier. A review of the literature was performed to determine the most appropriate modeling approach. A chemical kinetic model was chosen, and developed in MATLAB using the Newton-Raphson method to solve sets of 18 simultaneous equations. These equations account for mass and energy balances throughout the gasifier. The chemical kinetic rate expressions for these reactions were sourced from the literature, and some values modified to better fit the predicted gas composition to literature data.

[ES] Teniendo en cuenta el agotamiento de los combustibles fósiles y la creciente concentración de CO2 en la atmósfera, la hidrogenación de CO2 es una forma prometedora de convertir el CO2 en productos químicos y combustibles de carbono de alto valor añadido. Considerando la gran influencia del tamaño de partícula, la composición química, la naturaleza del soporte y las condiciones de operación sobre el comportamiento catalítico de los catalizadores, se han desarrollado una serie de catalizadores para la hidrogenación de CO2 basados en metales abundantes no nobles y polisacáridos naturales como precursores del grafeno. En la presente tesis doctoral, las especies metálicas soportadas sobre una matriz de carbono grafítico defectuosa, con diferentes tamaños de partículas, muestran diferente actividad catalítica y selectividad para la hidrogenación de CO2. Se prepararon, de forma controlada, nanopartículas de aleaciones de Co y Co-Fe soportadas en grafenos dopados con N defectuosos, con una amplia distribución de tamaño de nanopartículas, para la reacción de Sabatier, presentando una selectividad a metano superior al 90% con valores de conversión de CO2 superiores al 85%. En el caso de un solo metal, Co o Fe, y sus aleaciones en forma de "clusters" y pequeñas nanopartículas soportadas en el mismo material, la selectividad de la hidrogenación de CO2 cambia a CO, en lugar de metano, obteniéndose un valor del 98 % y alcanzando una conversión de CO2 del 56%. Conviene resaltar que, los catalizadores basados en "clusters" de aleaciones de metal con una carga de metal incluso por debajo del 0.2 % en peso, exhiben una mayor selectividad y rendimiento que los que tienen nanopartículas de aleaciones de Co-Fe más grandes que varían de 1 a 4 nm y una carga de metal más alta en una composición similar. Siguiendo la línea de investigación de hidrogenación de CO2, se desarrollaron una serie de nanopartículas de aleaciones de Co-Fe soportadas sobre grafenos dopados con N defectuosos con distribución de tamaño de nanopartículas controlada en el rango de 7-17 nm, obteniendo una selectividad hacia hidrocarburos C2+ alrededor del 45% y una conversión del CO2 cercana al 60%. Además, se realizó un estudio comparativo de la actividad catalítica de catalizadores similares basados en Co-Fe con promotores e inhibidores para la hidrogenación de CO2, observando su influencia en la conversión y selectividad de CO2. Finalmente, además de los catalizadores basados en Co-Fe, también se han preparado catalizadores basados en Cu-ZnO mediante un método de dos pasos. Estas nanopartículas de Cu-ZnO soportadas sobre grafeno defectuoso dopado con N exhiben una alta selectividad hacia la conversión de CO2 a metanol. / [CA] Tenint en compte l'esgotament dels combustibles fòssils i la creixent concentració de CO2 en l'atmosfera, la hidrogenació de CO2 és una forma prometedora de convertir el CO2 en productes químics i combustibles de carboni d'alt valor afegit. Considerant la gran influència de la grandària de partícula, la composició química, la naturalesa del suport i les condicions d'operació sobre el comportament catalític dels catalitzadors, s'han desenvolupat una sèrie de catalitzadors per a la hidrogenació de CO2 basats en metalls abundants no nobles i polisacàrids naturals com a precursors del grafé. En la present tesi doctoral, les espècies metàl·liques suportades sobre una matriu de carboni grafític defectuosa, amb diferents grandàries de partícules, mostren diferent activitat catalítica i selectivitat per a la hidrogenació de CO2. Es van preparar, de manera controlada, nanopartícules d'aliatges de Co i Co-Fe suportades en grafens dopats amb N defectuosos, amb una àmplia distribució de grandària de nanopartícules, per a la reacció de Sabatier, presentant una selectivitat a metà superior al 90% amb valors de conversió de CO2 superiors al 85%. En el cas d'un sol metall, Co o Fe, i els seus aliatges en forma de "clústers" i xicotetes nanopartícules suportades en el mateix material, la selectivitat de la hidrogenació de CO2 canvia a CO, en lloc de metà, obtenint-se un valor del 98% i aconseguint una conversió de CO2 del 56%. Convé ressaltar que, els catalitzadors basats en "clústers" d'aliatges de metall amb una càrrega de metall fins i tot per davall del 0.2% en pes, exhibeixen una major selectivitat i rendiment que els que tenen nanopartícules d'aliatges de Co-Fe més grans que varien d'1 a 4 nm i una càrrega de metall més alta en una composició similar. Seguint la línia d'investigació d'hidrogenació de CO2, es van desenvolupar una sèrie de nanopartícules d'aliatges de Co-Fe suportades sobre grafens dopats amb N defectuosos amb distribució de grandària de nanopartícules controlada en el rang de 7-17 nm, obtenint una selectivitat cap a hidrocarburs C2+ al voltant del 45% i una conversió del CO2 pròxima al 60%. A més, es va realitzar un estudi comparatiu de l'activitat catalítica de catalitzadors similars basats en Co-Fe amb promotors i inhibidors per a la hidrogenació de CO2, observant la seua influència en la conversió i selectivitat de CO2. Finalment, a més dels catalitzadors basats en Co-Fe, també s'han preparat catalitzadors basats en Cu-ZnO mitjançant un mètode de dos passos. Aquestes nanopartícules de Cu-ZnO suportades sobre grafé defectuós dopat amb N exhibeixen una alta selectivitat cap a la conversió de CO2 a metanol. / [EN] Considering the depletion of fossil fuels and the increasing atmospheric CO2 concentration, CO2 hydrogenation is a promising way to convert CO2 into value-added carbon-containing chemicals and fuels. Taking into account the significant influences of the particle size, chemical composition, nature of the support, and operation conditions on the catalytic performance of catalysts, a series of catalysts for CO2 hydrogenation have been developed based on the use of abundant non-noble metals and natural polysaccharides as graphene precursors. In the present PhD Thesis, metal species supported on defective graphitic carbon matrix with different particle sizes show different catalytic activity and selectivity for CO2 hydrogenation. Under effective control, Co and Co-Fe alloy nanoparticles wrapped on defective N-doped graphenes with a broad nanoparticle size distribution were prepared and performed for the Sabatier reaction, exhibiting a selectivity to methane over 90 % at CO2 conversion values over 85 %. In the case of single Co or Fe metal and their alloys in the form of clusters and small nanoparticles wrapped on the same support, the selectivity for CO2 hydrogenation shifts to CO, rather than methane, reaching a conversion of 56 % with 98 % CO selectivity. It is worth noting that the metal alloy clusters-based catalysts with the metal loading even below 0.2 wt.% exhibit a higher selectivity and better performance than the ones with larger Co-Fe alloy nanoparticles ranging from 1-4 nm and higher metal loading in a similar composition. Following the research line for CO2 hydrogenation, a series of Co-Fe alloy nanoparticles supported on defective N-doped graphenes with controlled nanoparticle size distribution in the range of 7-17 nm are developed, obtaining a selectivity towards C2+ hydrocarbons about 45% with a CO2 conversion close to 60%. In addition, a comparative catalytic activity of similar Co-Fe-based catalysts with promoters and poison has been studied for CO2 hydrogenation to observe their influence on CO2 conversion and selectivity. Finally, besides Co-Fe-based catalysts, Cu-ZnO-based catalysts have also been prepared by a two-step method. These Cu-ZnO nanoparticles supported on N-doped defective graphene exhibit a high selectivity for CO2 conversion to methanol. / Peng, L. (2021). Metal Nanoparticles Wrapped on Defective Nitrogen-doped Graphitic Carbons as Highly Selective Catalysts for C02 Hydrogenation [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/172329 / TESIS