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| 2. |
- Bauhn, Lovisa, 1981, et al.
(författare)
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The fate of hydroxyl radicals produced during H2O2 decomposition on a SIMFUEL surface in the presence of dissolved hydrogen
- 2018
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Ingår i: Journal of Nuclear Materials. - : Elsevier BV. - 0022-3115. ; 507, s. 38-43
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Tidskriftsartikel (refereegranskat)abstract
- Over geologic timescales hydrogen peroxide will be one of the most important radiolytic oxidants challenging the spent fuel integrity in a deep repository. Consequently, the reaction between hydrogen peroxide and different kinds of UO 2 based materials has been the subject of several studies over recent decades. Parts of these studies have investigated the effect of dissolved hydrogen on this reaction, as large amounts of hydrogen are expected to be produced by anoxic corrosion of iron in the deep repositories. In some of the studies hydrogen has been shown to offset the radiolysis-driven oxidative dissolution of the fuel despite the expected inertia of hydrogen at repository temperatures. However, the underlying mechanism is primarily based on the effect of the metallic particles contained in the spent fuel. One clue to the mechanistic understanding is whether or not a reaction takes place between dissolved hydrogen and hydroxyl radicals adsorbed to a fuel surface resulting from the decomposition of H 2 O 2 . In the study presented here this reaction could be confirmed in an autoclave system with SIMFUEL, a hydrogen peroxide spiked solution, and deuterium gas. The results show that the studied reaction does not only occur, but accounts for a substantial part of the hydrogen peroxide consumption in the system. Only a very minor part, 0.02%, of the total consumed hydrogen peroxide caused oxidative dissolution of the SIMFUEL. The conclusion is supported by quantitative measurements of HDO, dissolved U in solution and O 2 in the gas phase.
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| 3. |
- Corcoran, Angelica, 1988, et al.
(författare)
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Comparing the structural development of sand and rock ilmenite during long-term exposure in a biomass fired 12 MWth CFB-boiler
- 2018
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Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820. ; 171, s. 39-44
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Tidskriftsartikel (refereegranskat)abstract
- Oxygen Carrier Aided Combustion (OCAC) is a novel combustion concept with the purpose to increase the overall efficiency in conventional circulating fluidized bed (CFB) boilers. By replacing the commonly used bed material with an oxygen carrier (OC), the conceptual idea is to utilize the fluid dynamics in a CFB and the inherent oxygen transport supported by the OC to increase the oxygen distribution within the furnace in time and space. The OCAC concept has been successfully validated and further reached long-term demonstration in full scale operation (75-MW th ). This work presents a first evaluation of how ilmenite particles are affected in regard to mechanical resistance during long-term exposure to OCAC conditions in Chalmers 12-MW th CFB-boiler. A sand and a rock ilmenite are evaluated with regard to their mechanical stability. For evaluation, samples of the fresh materials and samples collected during operation in the Chalmers boiler are investigated. The study shows that the two materials differ in how the mechanical degradation occurs with exposure time. The sand ilmenite form cavities which are held together by an ash layer before they are shattered into numerous pieces, whereas the rock ilmenite develops distinct cracks that cause splitting of the particles.
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| 4. |
- Maric, Jelena, 1983, et al.
(författare)
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Valorization of Automobile Shredder Residue Using Indirect Gasification
- 2018
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 32:12, s. 12795-12804
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Tidskriftsartikel (refereegranskat)abstract
- Dual fluidized bed (DFB) gasification offers the possibility to convert solid fuels into a valuable gas, comprised of syngas, and hydrocarbons that can be readily handled in petrochemical units. DFB gasifiers are especially suitable for nonhomogeneous fuels, such as waste fractions. In this work, the possibility to use DFB gasification as a recycling/valorization method of automobile shredder residue is investigated. The gasification tests were carried out in the Chalmers 2–4 MWth gasifier over 4 days. The effects of ash on the gas and tar compositions, as well as on the activity of the bed inventory, were evaluated. The results show that 60% of the total carbon in the fuel can be recovered in the form of a permanent gas, whereby the produced gas contains 12%mol of C2–3 hydrocarbons. The tar levels measured in the produced gas were high, although it was clear that decomposition into monomer-like compounds occurred in the reactor, which resulted in the production of valuable petrochemical compounds, corresponding to 8–9% of the carbon in the feed. Using a higher operating temperature was found to be beneficial in terms of obtaining a higher gas yield, regardless of the level of ash enrichment in the system. The high ash levels in the fuel feed did not negatively affect the technical operation of the fluidized bed. Possible routes of carbon recovery are discussed.
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| 5. |
- Palme, Anna, 1986, et al.
(författare)
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Development of an efficient route for combined recycling of PET and cotton from mixed fabrics
- 2017
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Ingår i: Textiles and Clothing Sustainability. - : Springer Science and Business Media LLC. - 2197-9936. ; 3:4
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Tidskriftsartikel (refereegranskat)abstract
- Most textile waste is either incinerated or landfilled today, yet, the material could instead be recycled through chemical recycling to new high-quality textiles. A first important step is separation since chemical recycling of textiles requires pure streams. The focus of this paper is on the separation of cotton and PET (poly(ethylene terephthalate), polyester) from mixed textiles, so called polycotton. Polycotton is one of the most common materials in service textiles used in sheets and towels at hospitals and hotels. A straightforward process using 5–15 wt% NaOH in water and temperature in the range between 70 and 90 °C for the hydrolysis of PET was evaluated on the lab-scale. In the process, the PET was degraded to terephthalic acid (TPA) and ethylene glycol (EG). Three product streams were generated from the process. First is the cotton; second, the TPA; and, third, the filtrate containing EG and the process chemicals. The end products and the extent of PET degradation were characterized using light microscopy, UV-spectroscopy, and ATR FT-IR spectroscopy, as well as solution and solid-state NMR spectroscopy. Furthermore, the cotton cellulose degradation was evaluated by analyzing the intrinsic viscosity of the cotton cellulose. The findings show that with the addition of a phase transfer catalyst (benzyltributylammonium chloride (BTBAC)), PET hydrolysis in 10% NaOH solution at 90 °C can be completed within 40 min. Analysis of the degraded PET with NMR spectroscopy showed that no contaminants remained in the recovered TPA, and that the filtrate mainly contained EG and BTBAC (when added). The yield of the cotton cellulose was high, up to 97%, depending on how long the samples were treated. The findings also showed that the separation can be performed without the phase transfer catalyst; however, this requires longer treatment times, which results in more cellulose degradation.
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| 6. |
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| 7. |
- Arora, Prakhar, 1987
(författare)
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Catalytic Upgrading of Waste Oils to Advanced Biofuels – Deactivation and Kinetic Modelling Study
- 2018
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The demand for liquid hydrocarbons as transportation fuels is enormous and ever growing. Advanced biofuels is one of the promising solutions to keep pace with the global transition to cleaner energy by reducing greenhouse gas emissions from the transport sector. It is possible to selectively remove oxygen from waste oils like tall oil, used cooking oil etc. via a catalytic hydrodeoxygenation (HDO) process to produce advanced biofuels. These biofuels have similar molecules as in the traditional fossil-based fuels and exhibit improved performance. This thesis focuses on aspects of catalyst deactivation and kinetic modelling of HDO reactions. In the first study, the influence of iron (Fe) as a poison during HDO of a model compound for renewable feeds (Oleic acid) over molybdenum based sulfided catalysts was investigated. Fe is a potential contaminant in renewable feeds due to corrosion during transportation and storage in iron vessels. A series of experiments with varying Fe-oleate concentration in the feed over MoS2/Al2O3 and NiMoS/Al2O3 catalysts. There was a salient drop in the activity of the catalysts. At higher Fe concentration, for the NiMoS catalyst, the selectivity for the direct hydrodeoxygenation product (C18 hydrocarbons) increased. However, it was opposite for the MoS2 catalyst. There was a decrease in the yield of direct hydrodeoxygenation products and an increase in yield of decarbonated products. It was proposed that Fe interacted with these two catalyst systems differently. Fe influenced the critical step of creation of sulfur vacancies in a negative way which resulted in lower activity. Microscopic analysis indicated that Fe was preferentially deposited close or around the nickel promoted phase, which explained why the role of Ni as a promoter for the decarbonation route was subdued for the NiMoS catalyst. In the second study, the kinetics during HDO of stearic acid (SA) over a sulfided NiMo/Al2O3 catalyst were explored to investigate the reaction scheme. Model compounds like octadecanal (C18=O) and octadecanol (C18-OH) were employed to understand the reaction steps and quantify the selectivity. A Langmuir–Hinshelwood-type kinetic model was used to investigate the kinetics. The results from the proposed kinetic model were found to be in good agreement with experimental results. In addition, the model could effectively reproduce the observed experimental profiles of different intermediates like C18=O and C18-OH and illustrate phenomena like inhibiting effects of the fatty acid.
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| 8. |
- Arora, Prakhar, 1987
(författare)
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Deactivation of Catalysts and Reaction Kinetics for Upgrading of Renewable Oils
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The transport sector is one of the main contributors of greenhouse gas emissions in the world. Advanced biofuels from renewable oils can play a decisive role in reducing carbon emissions from the transport sector. Advanced biofuels from waste streams like tall oil, used cooking oil etc. can lower the CO2 emissions in a range of up to 90% making our future and society more sustainable. Catalytic hydrodeoxygenation (HDO) is a process in which oxygen is selectively removed from renewable oils to produce advanced biofuels. These biofuels are drop-in hydrocarbons which can substitute fossil-based fuels without infrastructure or vehicle changes. This thesis focuses on aspects of catalyst deactivation and reaction kinetics during the production of such biofuels via HDO reactions. Renewable oils can be sourced from varied streams like tall oil (paper industry residue), animal fats, used cooking oil etc. due to which their composition and innate contaminants can vary significantly. Phosphorus, alkali metals like potassium or sodium, iron, silicon, chlorides etc. are some of the common poisons present in renewable feedstocks which can cause catalyst deactivation during the upgrading process. In the first section of this thesis, the influence of iron (Fe), phosphorus (from phospholipid) and potassium (K) as poisons during HDO of fatty acids over molybdenum based sulfided catalysts was investigated. A range of concentration of poisons was evaluated to show that these poisons severely impacted the activity of catalysts. A change in selectivity was also seen, which is an important parameter to consider during the industrial production of biofuels. Different characterization techniques were employed to study the poison distribution on catalyst samples from lab experiments as well as from a refinery. It was suggested that Fe deposits preferentially near Ni-rich sites which deteriorated the ability of these catalysts to create active sites i.e. via sulfur vacancies. However, phosphorus resulted in irreversible phase transformation of the support to aluminum phosphate (AlPO4) which resulted in catalyst deactivation via pore blockage. In the comparative experiments, with spherical catalyst particles (1.8 mm), the Fe caused the strongest deactivation among P and K, based on the quantity added to feed oil. Although, considering the decrease in surface area per unit of deposited element after the experiment, then P caused the most deactivation. It was concluded that Fe deposited mostly near to the outer surface irrespective of concentration while P and K penetrated deeper in catalyst particles such that the distribution profile was dependent on the concentration. Reaction kinetics of HDO of fatty acids provides critical knowledge which could be applied at the refining scale in process design and optimization. The activity and selectivity of NiMo catalyst during HDO of stearic acid was studied by varying reaction conditions like temperature, pressure, feed concentration and batch-reactor stirring rate and using intermediates like octadecanal and octadecanol. A deeper understanding of the reaction scheme and selectivities was developed based on the experimental results. A Langmuir–Hinshelwood-type mechanism was used to develop a kinetic model which well-predicted the changes in selectivities at varying reaction conditions.
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| 9. |
- Auvray, Xavier, 1986, et al.
(författare)
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Aging of Cu/SSZ-13 for NH3 SCR in mixed lean condition
- 2018
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- Two catalytic methods have been developed to remove the NOx emissions from diesel vehicles and comply with the emission regulations: the NOx storage and reduction process (NSR) and the reduction of NOx with NH3 (SCR). Advanced systems combining these two methods for an optimum efficiency are now studied. SCR catalysts are subjected alternating lean and rich conditions as well as to high temperatures in rich conditions during deSOx of the LNT material. The purpose of the present work is therefore to determine the response of a Cu/SSZ-13 to several aging treatments at 800°C involving rich and/or lean exposure. Deactivation was observed after all types of aging. However strong differences in deactivation degree exists between aging procedures. Lean aging, for 8h at 800°C, was the most moderate aging tested although it brought about significant activity loss below 250°C. Alternating between long lean periods and short rich periods caused slightly stronger deactivation, which was most significant at 200°C. However, the switching frequency between lean and rich had negligible influence on subsequent activity. As shown in Figure 1, SCR activity after 8h exposure in H2 was outstandingly low. It increased monotonically with temperature to reach a maximum of 58% NO conversion. Further investigation pertaining to the rich treatment was performed. The aging time was reduced to 2h and, for direct comparison, a 32h cycling aging was performed, implying a total rich time of 2h. Both samples were severely impacted over the whole temperature range. It revealed that 2h in rich conditions led to stronger deactivation than 8h in lean and lean/rich conditions, emphasizing the deterioration power of H2. Aging caused by rich conditions was so dominant that additional 30h in lean has negligible influence on SCR below 300°C. However, the long additional exposure to lean conditions lowered significantly the SCR activity between 400 and 500°C.
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| 10. |
- Bac, Selin, et al.
(författare)
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Exceptionally active and stable catalysts for CO2 reforming of glycerol to syngas
- 2019
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Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373 .- 1873-3883. ; 256
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Tidskriftsartikel (refereegranskat)abstract
- CO2 reforming of glycerol to syngas was studied on Al2O3-ZrO2-TiO2 (AZT) supported Rh, Ni and Co catalysts within 600–750 °C and a molar inlet CO2/glycerol ratio (CO2/G) of 1–4. Glycerol and CO2 conversions decreased in the following order: Rh/AZT > Ni/AZT > Co/AZT. Reactant conversions on Rh/AZT exceeded 90% of their thermodynamic counterparts at 750 °C and CO2/G = 2–4 at which the activity of Ni/AZT was boosted to ˜95% of the thermodynamic CO2 conversion upon increasing the residence time. The loss in CO2 conversions was below 13% during the 72 h longevity tests confirming the exceptional stability of Rh/AZT and Ni/AZT. However, Co/AZT suffered from sintering, carbon deposition and oxidation of Co sites, demonstrated via TEM-EDX, XPS, XANES and in-situ FTIR experiments. Characterization of Rh/AZT revealed no significant signs of deactivation. Ni/AZT preserved most of its original metallic pattern and gasified carbonaceous deposits during earlier stages of the reaction.
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