| 1. |
- H. Moud, Pouya, et al.
(författare)
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Biomass pyrolysis gas conditioning over an iron-based catalyst for mild deoxygenation and hydrogen production
- 2017
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Ingår i: Fuel. - : Elsevier BV. - 0016-2361 .- 1873-7153. ; 211, s. 149-158
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Bio-crude is a renewable source for production of valuable energy carriers. Prior to its utilization, a conditioning step of the raw pyrolysis gas can be beneficial before the bio-crude is converted via catalytic hydrodeoxygenation (HDO) into liquid hydrocarbon products, or via steam reforming (SR) to synthesis gas/hydrogen. An experimental small industrial scale study for the chemistry of atmospheric pressure pyrolysis gas conditioning resulting in bio-crude deoxygenation and a hydrogen-rich gas using an iron-based catalyst without addition of hydrogen or steam is presented and discussed. Following a short catalyst stabilization period with fluctuating bed temperatures, the catalyst operated near 450°C at a space velocity of 1100 h-1 for 8 hours under stable conditions during which no significant catalyst deactivation was observed. Experimental results indicate a 70-80% reduction of acetic acid, methoxy phenols, and catechol, and a 55-65% reduction in non-aromatic ketones, BTX, and heterocycles. Alkyl phenols and phenols were least affected, showing a 30-35% reduction. Conditioning of the pyrolysis gas resulted in a 56 % and a 18 wt% increase in water and permanent (dry) gas yield, respectively, and a 29 % loss of condensable carbon. A significant reduction of CO amount (-38 %), and production of H2 (+1063 %) and CO2 (+36 %) over the catalyst was achieved, while there was no or minimal change in light hydrocarbon content. Probing the catalyst after the test, the bulk phase of the catalyst was found to be magnetite (Fe3O4) and the catalyst exhibited significant water gas shift (WGS) reaction activity. The measured gas composition during the test was indicative of no or very limited Fischer-Tropsch (FT) CO /CO2 hydrogenation activity and this infers that also the active surface phase of the catalyst during the test was Fe-oxide, rather than Fe-carbide. The results show that iron-based materials are potential candidates for application in a pyrolysis gas pre-conditioning step before further treatment or use, and a way of generating a hydrogen-enriched gas without the need for bio-crude condensation.
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| 2. |
- H. Moud, Pouya
(författare)
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Catalytic Conversion of Undesired Organic Compounds to Syngas in Biomass Gasification and Pyrolysis Applications
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Reliable energy supply is a major concern and crucial for development of the global society. To address the dependency on fossil fuel and the negative effects of this reliance on climate, there is a need for a transition to cleaner sources. An attractive solution for replacing fossil-based products is renewable substitutes produced from biomass. Gasification and pyrolysis are two promising thermochemical conversion technologies, facing challenges before large-scale commercialization becomes viable. In case of biomass gasification, tar is often and undesired by-product. An attractive option to convert tar into syngas is nickel-based catalytic steam reforming (SR). For biomass pyrolysis, catalytic SR is in early stages of investigation as a feasible option for bio-crude conversion to syngas.The focus of the thesis is partly dedicated to describe research aimed at increasing the knowledge around tar reforming mechanisms and effect of biomass-derived impurities on Ni-based tar reforming catalyst downstream of gasifiers. The work focuses on better understanding of gas-phase alkali interaction with Ni-based catalyst surface under realistic conditions. A methodology was successfully developed to enable controlled investigation of the combined sulfur (S) and potassium (K) interaction with the catalyst. The most striking result was that K appears to lower the sulfur coverage and increases methane and tar reforming activity. Additionally, the results obtained in the atomistic investigations are discussed in terms of naphthalene adsorption, dehydrogenation and carbon passivation of nickel.Furthermore, the thesis describes research performed on pyrolysis gas pre-conditioning at a small-industrial scale, using an iron-based catalyst. Findings showed that Fe-based materials are potential candidates for application in a pyrolysis gas pre-conditioning step before further treatment or use, and a way for generating a hydrogen-enriched gas without the need for bio-crude condensation.
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| 3. |
- Haghighi Moud, Pouya, et al.
(författare)
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Equilibrium potassium coverage and its effect on a Ni tar reforming catalyst in alkali- and sulfur-laden biomass gasification gases
- 2016
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Ingår i: Applied Catalysis B. - : Elsevier. - 0926-3373 .- 1873-3883. ; 190, s. 137-146
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Tidskriftsartikel (refereegranskat)abstract
- Biomass conversion to syngas via gasification produces certain levels of gaseous by-products, such as tar and inorganic impurities (sulfur, potassium, phosphorus etc.). Nickel, a commonly used catalyst for hydrocarbqn steam reforming, suffers reduced reforming activity by small amounts of sulfur (S) or potassium (K), while resistance against deleterious carbon whisker formation increases. Nevertheless, the combined effect of biomass derived gas phase alkali at varying concentrations together with sulfur on tar reforming catalyst performance under realistic steady-state conditions is largely unknown. Prior to this study, a methodology to monitor these effects by precise K dosing as well as K co-dosing with S was successfully developed. A setup consisting of a 5 kW biomass fed atmospheric bubbling fluidized bed gasifier, a high temperature hot gas ceramic filter, and a catalytic reactor operating at 800 degrees C were used in the experiments. Within the current study, two test periods were conducted, including 30 h with 1 ppmv potassium chloride (KCl) dosing followed by 6 h without KCl dosing. Besides an essentially carbon-free operation, it can be concluded that although K, above a certain threshold surface concentration, is known to block active Ni sites and decrease activity in traditional steam reforming, it appears to lower the surface S coverage (theta(s)) at active Ni sites. This reduction in theta(s) increases the conversion of methane and aromatics in tar reforming application, which is most likely related to K-induced softening of the S-Ni bond. The K-modified support surface may also contribute to the significant increase in reactivity towards tar molecules. In addition, previously unknown relevant concentrations of K during realistic operating conditions on typical Ni-based reforming catalysts are extrapolated to lie below 100 mu K/m(2), a conclusion based on the 10-40 mu K/m(2) equilibrium coverages observed for the Ni/MgAl2O4 catalyst in the present study.
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| 4. |
- Hernandez, Asbel, et al.
(författare)
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Gas-Phase Potassium Effects and the Role of the Support on the Tar Reforming of Biomass-Derived Producer Gas Over Sulfur-Equilibrated Ni/MgAl2O4
- 2020
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Ingår i: Energy & Fuels. - : American Chemical Society. - 0887-0624 .- 1520-5029. ; 34:9, s. 11103-11111
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Tidskriftsartikel (refereegranskat)abstract
- Biomass gasification is a sustainable way to convert biomass residues into valuable fuels and chemicals via syngas production. However, several gas impurities need to be removed before the final synthesis. Understanding of the interactions and effects of biomass-derived producer gas contaminants (S and K) on the performance of reforming catalysts is of great importance when it comes to process reliability and development. In the present study, the steam reforming activity at 800 °C of a sulfur-equilibrated nickel catalyst during controlled exposure to alkali species (∼2 ppmv K) and in its absence was investigated using real producer gas from a 5 kWth O2-blown fluidized-bed gasifier. Conversions of CH4, C2H4, and C10H8 were used to evaluate the performance of the Ni/MgAl2O4 catalyst and MgAl2O4 support. A significant and positive effect on the catalyst activity is observed with addition of gas-phase KCl. This is assigned primarily to the observed K-induced reduction in sulfur coverage (θS) on Ni—an effect which is reversible. The catalytic contribution of the K-modified pure MgAl2O4 support was found to be significant in the conversion of naphthalene but not for light hydrocarbons. The product and catalyst analyses provided evidence to elucidate the preferential adsorption site for S and K on the catalyst as well as the role of the support. Whereas S, as expected, was found to preferentially adsorb on the surface of Ni particles, forming S-Ni sites, K was found to preferentially adsorb on the MgAl2O4 support. A low but still significant K adsorption on S–Ni sites, or an effect on only the fraction of exposed Ni surface area near the metal–support interface, can, however, not be excluded. The result suggests that an improved Ni/MgAl2O4 catalyst activity and an essentially carbon-free operation can be achieved in the presence of controlled amount of gas-phase potassium and high sulfur coverages on Ni. Based on the results, a mechanism of the possible K–S interactions is proposed.
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| 5. |
- Hernandez, Asbel, et al.
(författare)
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Preferential adsorption of K species and the role of support during reforming of biomass derived producer gas over sulfur passivated Ni/MgAl2O4
- 2020
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Ingår i: Energy & Fuels. - 0887-0624 .- 1520-5029. ; 34:9, s. 11103-11111
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Tidskriftsartikel (refereegranskat)abstract
- Biomass gasification is a sustainable way to convert biomass residues into valuable fuels and chemicals via syngasproduction. However, several gas impurities need to be removed before thefinal synthesis. Understanding of the interactions andeffects of biomass-derived producer gas contaminants (S and K) on the performance of reforming catalysts is of great importancewhen it comes to process reliability and development. In the present study, the steam reforming activity at 800°C of a sulfur-equilibrated nickel catalyst during controlled exposure to alkali species (∼2 ppmv K) and in its absence was investigated using realproducer gas from a 5 kWthO2-blownfluidized-bed gasifier. Conversions of CH4,C2H4, and C10H8were used to evaluate theperformance of the Ni/MgAl2O4catalyst and MgAl2O4support. A significant and positive effect on the catalyst activity is observedwith addition of gas-phase KCl. This is assigned primarily to the observed K-induced reduction in sulfur coverage (θS)onNianeffect which is reversible. The catalytic contribution of the K-modified pure MgAl2O4support was found to be significant in theconversion of naphthalene but not for light hydrocarbons. The product and catalyst analyses provided evidence to elucidate thepreferential adsorption site for S and K on the catalyst as well as the role of the support. Whereas S, as expected, was found topreferentially adsorb on the surface of Ni particles, forming S-Ni sites, K was found to preferentially adsorb on the MgAl2O4support.A low but still significant K adsorption on S−Ni sites, or an effect on only the fraction of exposed Ni surface area near the metal−support interface, can, however, not be excluded. The result suggests that an improved Ni/MgAl2O4catalyst activity and anessentially carbon-free operation can be achieved in the presence of controlled amount of gas-phase potassium and high sulfurcoverages on Ni. Based on the results, a mechanism of the possible K−S interactions is proposed
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| 8. |
- Ahmadi, Mozhgan, et al.
(författare)
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Application of Solid-Phase Microextraction (SPME) as a Tar Sampling Method
- 2013
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 0887-0624 .- 1520-5029. ; 27:7, s. 3853-3860
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Tidskriftsartikel (refereegranskat)abstract
- This paper presents the result of an investigation of the potential use of solid-phase microextraction (SPME) as a tar sampling method. The SPME stationary phase used was 50 mu m of polydimethylsiloxane (PDMS) coated on a fused silica fiber. Tar model compounds normally present in a producer gas from gasifiers, benzene, toluene, indane, indene, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene, were used in the investigation. The adsorbed compounds were analyzed by injection into gas chromatography coupled to a flame ionization detector (GC- FID). The amount of adsorbed tar on the SPME fiber determined the detection and quantification limits for the method. The results showed that adsorption of tar model compounds on the SPME fiber increased with decreasing polarity. The adsorption of compounds increased with a decreasing temperature, enabling a possibility to tune the sensitivity of the method by changing the sampling temperature. Conclusively, SPME has a very high potential as a tar sampling method and, in combination with GC- FID trace analysis of tar, is a feasible application.
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