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.

This thesis work has been conducted in the Handheld Laboratory at Husqvarna AB with the purpose of finding the parameters responsible for the performance of the catalytic converters used in the test rig. The catalytic converters are used in the test rig during the long term testing of the chain saws to reduce the hydrocarbon content from the exhaust before it enters into the environment.   To perform this research two approaches were carried out. One with Design of Experiment (DOE) and another using Scanning Electron Microscope (SEM) analysis. In Design of Experiments parameters that are suspected to be influencing the performance of the catalytic converter were refined. Using these parameters a test plan is made with the help of statistical analysis application Minitab and the tests were carried out in the test rig. Using SEM the effects of aging and its effect on microstructure and chemical composition on the catalyst surface was analyzed. The results from the DoE shows that the exhaust flow, collector diameter and distance to the muffler are responsible for the collection of exhaust. Distance to the muffler and collector length are the factors affecting the conversion of the exhaust. In addition to that exhaust flow is also responsible for the duration of heating coil running time.        The results from the SEM analysis shows that the operating temperature is high due to which there is thermal degradation of catalyst and there is also deactivation due to fouling. Another finding is that the flow on to the catalyst is not uniformly distributed

Various distillates are treated with hydrogen gas during hydrotreatment in the presence of catalyst in order to reduce the sulfur and aromatic content of the product. Optimal hydrotreater performance is essential for producing Nynas specialty oils, in order to fulfill the planned production volume and to meet the product specification. Loss of catalyst activity is inevitable during the production. To adjust for the impact of catalyst deactivation, different process variables are manipulated. Different distillates affect the catalyst in different ways due to the variation in distillate composition. Distillates with higher organic nitrogen content and running at a lower temperature tend to deactivate the catalyst more due to the adsorption of nitrogen compounds on the active sites of the catalyst and their slow nature of desorption. In this master thesis, different catalyst deactivation mechanisms with a focus on nitrogen deactivation have been studied. Since nitrogen is not normally measured at Nynas, nitrogen content of different distillates and products and how these values change during operation was not known. Different distillates, blend of distillates and different products were measured to estimate roughly the typical nitrogen value of the distillates and products. The temperature data inside the reactors were analyzed to calculate and plot WABT (weighted average bed temperature) during different product runs and to see whether there is a correlation between the nitrogen content of the feed and operation severity (increase in WABT). Historical process data from hydrotreater unit 2 (mostly from 2013-2014) were analyzed with a view to finding out signs of catalyst deactivation. Similar product runs were also analyzed and compared to see how the catalysts performed at different periods of time. A kinetic model, based on HDS kinetics, has been used for following up two product runs. To do so, sulfur content of the feed and product were measured. Aromatic content of the product was also measured to see whether the product was on specification. .From the calculation and plotting of WABTs, it could be seen that there is an increase in WABT during the product runs operating at lower temperatures and with higher nitrogen content. From the comparison of two P3 product runs at two different time periods, it could be seen that ∆T development over one bed (amount of reaction over the bed) was much lower at one time. This can possibly be a sign of catalyst deactivation since it contributed to lesser amount of reaction over the bed. From the calculations by using the kinetic model, it could be seen that the actual temperatures were higher than the predicted temperatures. The increase in WABTs could also be noticed. These observations can possibly be coupled with nitrogen deactivation of the catalysts.  However, more tests are required to verify whether the temperature differences were significant or not. Other parameters which are also important from product selling point of view such as viscosity, color, flash point, acid number etc. and have not been covered in this degree project need to be taken into consideration before making further conclusions.

Ce travail rapporte l’étude des processus de désactivation et des modifications d’un catalyseur Ir supportésur cérine en vaporeformage de l’éthanol. Différentes causes de désactivation ont été identifiées selon lesconditions opératoires : température, temps de contact et temps de réaction. La désactivation initiale,rapide mais limitée a été attribuée à la restructuration de surface de la cérine et à la formation d’unemonocouche d’intermédiaires de type acetate, carbonate et hydroxyls. En parallèle, une désactivationlente et progressive a été mise en évidence, ayant pour origine les changements structurels de l’interfaceentre la cérine et l’iridium, liés au frittage des particules d’iridium et à la restructuration profonde de lacérine. Par contre, la formation continue, à température modérée, d’une couche de carbone encapsulantissu de la polymérisation d’intermédiaires C2 n’a pas semblé contribuer significativement à ladésactivation du catalyseur dans nos conditions opératoires. Pour limiter ce phénomène de désactivation,des modifications ont été apportées au catalyseur. Le dopage du catalyseur par PrOx a permis defortement améliorer la capacité de stockage de l’oxygène et la stabilité thermique du catalyseur,entraînant une augmentation de son activité et de sa stabilité en vaporeformage de l’éthanol. Lecatalyseur Ir/CeO2 a ensuite subi une mise en forme de la cérine (nano-tubes), avec une influencesignificative sur l'activité et la stabilité en vaporeformage de l’éthanol, liée à des effets structuraux. Unemodélisation simplifiée de ces divers phénomènes a également contribué à soutenir les propositionsoriginales de ce travail. / The objective of the thesis was to analyze the ageing processes and the modifications of an Ir/CeO2catalyst for steam reforming of ethanol. Over a model Ir/CeO2 catalyst, the initial and fast deactivationwas ascribed to ceria surface restructuring and the build-up of intermediates monolayer (acetate,carbonate and hydroxyl groups). In parallel, a progressive and slow deactivation was found to come fromthe structural changes at the ceria/Ir interface linked to Ir sintering and ceria restructuring. Theencapsulating carbon, coming from C2 intermediates polymerization, did not seem too detrimental to theactivity in the investigated operating conditions. By doping ceria with PrOx, the oxygen storage capacityand thermal stability were greatly promoted, resulting in the enhanced activity and stability. The Ir/CeO2catalyst was then modified by changing the shape of ceria. It was found that the shape and therefore thestructure of ceria influenced the activity and stability significantly. A simplified modeling of theseprocesses has contributed to support the new proposals of this work.

No description available.

The effect of microwave radiation on the prepared 0.5Fe/ZSM-5 catalysts as a post-synthesis modification step was studied in the methanol-to-hydrocarbons process using the temperature-programmed surface reaction (TPSR) technique. This was achieved by preparing a series of 0.5Fe/ZSM-5 based catalysts under varying microwave power levels (0–700 W) and over a 10 s period, after iron impregnating the HZSM-5 zeolite (Si/Al = 30 and 80). Physicochemical properties were determined by XRD, SEM, BET, FT-IR, C3H9N-TPSR, and TGA techniques. It was found that microwave radiation induced few changes in the bulk properties of the 0.5Fe/ZSM-5 catalysts, but their surface and catalytic behavior were distinctly changed. Microwave radiation enhanced crystallinity and mesoporous growth, decreased coke and methane formation, decreased the concentration of Brønsted acidic sites, and decreased surface area and micropore volume as the microwave power level was increased from 0 to 700 W. From the TPSR profiles, it was observed that microwave radiation affects the peak intensities of the produced hydrocarbons. Application of microwave radiation shifted the desorption temperatures of the MTH process products over the HZSM-5(30) and HZSM-5(80) based catalysts to lower and higher values respectively. The MeOH-TPSR profiles showed that methanol was converted to DME and subsequently converted to aliphatic and aromatic hydrocarbons. It is reasonable to suggest that microwave radiation would be an essential post-synthesis modification step to mitigate coke formation and methane formation and increase catalyst activity and selectivity. / Chemical Engineering / M. Tech. (Chemical Engineering)