| 1. |
- Bergvall, Niklas, et al.
(författare)
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Corefining of Fast Pyrolysis Bio-Oil with Vacuum Residue and Vacuum Gas Oil in a Continuous Slurry Hydrocracking Process
- 2020
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Ingår i: Energy & Fuels. - : American Chemical Society. - 0887-0624 .- 1520-5029. ; 34:7, s. 8452-8465
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Tidskriftsartikel (refereegranskat)abstract
- Integration of renewable raw materials in existing refineries is most likely the shortest way for the successful, large-scale introduction of biofuels in the transport sector in the short term and medium term. One possible renewable raw material for this application is fast pyrolysis bio-oil (FPBO), which in this study has been coprocessed (at 0 and 20 wt %) with vacuum residue (VR, 50 wt %) and vacuum gas oil (VGO, balance) in a continuous, as well as a semibatch, slurry hydrocracking process. Experiments both with and without FPBO were performed at 450°C and 150 bar with a continuous hydrogen flow through the reactor. Oil-soluble molybdenum hexacarbonyl and molybdenum 2-ethylhexanoate were used as catalyst precursors, to be sulfided in situ. The continuous trials resulted in reactor walls completely free of coking, and they resulted in a low overall coke yield (about 1 wt %). The hydrodeoxygenation reached almost 92%, and the total acid number was reduced by nearly 99% in the FPBO experiment A mass balance of the renewable carbon from FPBO, based on the performed experiments, showed that the fossil CO2 emissions can be lowered by 1.35 kg per kg of processed FPBO if all renewable carbon in gaseous and liquid hydrocarbons is used to replace its fossil counterparts, and all methane formed from FPBO is used to produce hydrogen. Semibatch experiments gave less successful results when upgrading FPBO-containing feedstock, with a high coke yield (8 wt %) as well as a high gas yield (24 wt %). The results of this study demonstrate that FPBO can be successfully coprocessed with heavy fossil oils in a continuous slurry hydrocracking process without neg. affecting the processing of the fossil components of the feed and that a continuous process is preferred over batch or semibatch processes when studying coprocessing of bio-oils.
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| 2. |
- Carvalho, Lara, et al.
(författare)
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Alkali enhanced biomass gasification with in situ S capture and a novel syngas cleaning : Part 2: Techno-economic analysis
- 2018
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Ingår i: Energy. - : Elsevier. - 0360-5442 .- 1873-6785. ; 165:Part B, s. 471-482
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Tidskriftsartikel (refereegranskat)abstract
- Previous research has shown that alkali addition has operational advantages in entrained flow biomass gasification and allows for capture of up to 90% of the biomass sulfur in the slag phase. The resultant low-sulfur content syngas can create new possibilities for syngas cleaning processes. The aim was to assess the techno-economic performance of biofuel production via gasification of alkali impregnated biomass using a novel gas cleaning systemcomprised of (i) entrained flow catalytic gasification with in situ sulfur removal, (ii) further sulfur removal using a zinc bed, (iii) tar removal using a carbon filter, and (iv) CO2 reductionwith zeolite membranes, in comparison to the expensive acid gas removal system (Rectisol technology). The results show that alkali impregnation increases methanol productionallowing for selling prices similar to biofuel production from non-impregnated biomass. It was concluded that the methanol production using the novel cleaning system is comparable to the Rectisol technology in terms of energy efficiency, while showing an economic advantagederived from a methanol selling price reduction of 2–6 €/MWh. The results showed a high level of robustness to changes related to prices and operation. Methanol selling prices could be further reduced by choosing low sulfur content feedstocks.
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| 3. |
- Grahn, Mattias, et al.
(författare)
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Small ZSM-5 crystals with low defect density as an effective catalyst for conversion of methanol to hydrocarbons
- 2020
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Ingår i: Catalysis Today. - : Elsevier B.V.. - 0920-5861 .- 1873-4308. ; 345, s. 136-146
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Tidskriftsartikel (refereegranskat)abstract
- This work presents the synthesis of nearly defect-free ZSM-5 nanosized crystals, prepared in fluoride medium by seeding with silicalite-1. This material was carefully characterized and its catalytic performances in the methanol to hydrocarbons (MTH) reaction were assessed. Such fluoride-based material was compared to a reference ZSM-5, produced through a conventional alkaline synthesis but from the same seeding. Despite both the materials show closely identical morphology and they have a comparable acid site population, the catalyst prepared using the fluoride route showed significantly longer lifetime in MTH compared to the catalyst prepared using conventional synthesis at high pH. The slower deactivation for the samples prepared using the fluoride route was ascribed, thanks to a thorough in situ IR spectroscopy study, to its lower density of internal defects. According to the UV-Raman characterization of coke on the spent catalyst, the fluoride-based ZSM-5 catalyst produces less molecular coke species, most probably because of the absence of enlarged cavities/channels as due to the presence of internal defects. On the basis of these observations, the deactivation mechanism in the ZSM-5 synthesized by fluoride medium could be mostly related to the deposition of an external layer of bulk coke, whereas in the alkali-synthesized catalyst an additional effect from molecular coke accumulating within the porous network accelerates the deactivation process.
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| 4. |
- Hedlund, Jonas, et al.
(författare)
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Controlling diffusion resistance, selectivity and deactivation of ZSM-5 catalysts by crystal thickness and defects
- 2022
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Ingår i: Journal of Catalysis. - : Elsevier. - 0021-9517 .- 1090-2694. ; 410, s. 320-332
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Tidskriftsartikel (refereegranskat)abstract
- A systematic investigation of two sets of defect free and defective ZSM-5 crystals with controlled thickness (T) between 30 and 400 nm and of their performances in methanol conversion was reported for the first time in the present work. The defect free ZSM-5 crystals with a thickness of 35 nm are by far the smallest ever reported and displayed superior activity, stability and selectivity to slower diffusing compounds, which resulted in high yield of e.g. gasoline and the 1,2,4-trimethylbenzene isomer with high octane number, as compared to the other studied catalysts. Almost only products forming in the zeolite pores were detected and consequently, the external surface must be nearly inactive. Strong correlations between T and deactivation rate were observed. Thick crystals deactivated much faster than thin crystals, probably due to formation of carbon species in the zeolite pores, which results in pronounced percolation effects and faster deactivation of the former. At comparable thickness, crystals with defects deactivated much faster than defect free crystals, due to formation of additional small molecular coke species in the former. Strong correlations between T and selectivity were also observed and assigned to control of diffusion resistance by crystal thickness.
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| 5. |
- Johansson, Ann-Christine, et al.
(författare)
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Characterization of pyrolysis products produced from different Nordic biomass types in a cyclone pilot plant
- 2016
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Ingår i: Fuel processing technology. - : Elsevier. - 0378-3820 .- 1873-7188. ; 146, s. 9-19
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Tidskriftsartikel (refereegranskat)abstract
- Pyrolysis is a promising thermochemical technology for converting biomass to energy, chemicals and/or fuels. The objective of the present paper was to characterize fast pyrolysis products and to study pyrolysis oil fractionation. The products were obtained from different Nordic forest and agricultural feedstocks in a pilot scale cyclone pyrolysis plant at three different reactor temperatures. The results show that the main elements (C, H and O) and chemical compositions of the products produced from stem wood, willow, forest residue and reed canary grass are in general terms rather similar, while the products obtained from bark differ to some extent. The oil produced from bark had a higher H/Ceff ratio and heating value which can be correlated to a higher amount of pyrolytic lignin and extractives when compared with oils produced from the other feedstocks. Regardless of the original feedstock, the composition of the different pyrolysis oil fractions (condensed and aerosol) differs significantly from each other. However this opens up the possibility to use specifically selected fractions in targeted applications. An increased reactor temperature generally results in a higher amount of water and water insoluble material, primarily as small lignin derived oligomers, in the produced oil.
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| 6. |
- Johansson, Ann-Christine, et al.
(författare)
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Experiences of pilot scale cyclone pyrolysis
- 2017
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Ingår i: European Biomass Conf. Exhib. Proc.. - : ETA-Florence Renewable Energies. ; , s. 952-955
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Konferensbidrag (refereegranskat)abstract
- Fast pyrolysis is a promising thermochemical technology for converting biomass to energy, chemicals, and fuels. At RISE ETC, an industrially relevant pyrolysis pilot plant has been designed, constructed, and operated since 2011. The pilot plant is based on an externally heated cyclone reactor where both the pyrolysis reaction and the separation of products take place. The reactor design has shown to be beneficial since it produces oil with relatively low concentrations of inorganics. Pyrolysis of different Nordic biomasses, both forestry and agricultural, have been studied using the pilot plant and the results indicate that it is especially suitable for low grade fuels. The oil is collected in two separate steps, and the received two oil fractions have different chemical and physical properties, which opens up the possibility to use selected fractions in targeted applications. Oil fractionation has also been studied further in a separate fractional condensation system and the results show that it is possible to separate larger energy-rich lignin-derived material; medium-sized; and light water soluble compounds already in the oil collection step. The pilot plant has worked as a platform for pyrolysis research and for building up competence in the pyrolysis area.
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| 7. |
- Johansson, Ann-Christine, et al.
(författare)
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Fractional condensation of pyrolysis vapors produced from Nordic feedstocks in cyclone pyrolysis
- 2017
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Ingår i: Journal of Analytical and Applied Pyrolysis. - : Elsevier BV. - 0165-2370 .- 1873-250X. ; 123, s. 244-254
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Tidskriftsartikel (refereegranskat)abstract
- Pyrolysis oil is a complex mixture of different chemical compounds with a wide range of molecular weights and boiling points. Due to its complexity, an efficient fractionation of the oil may be a more promising approach of producing liquid fuels and chemicals than treating the whole oil. In this work a sampling system based on fractional condensation was attached to a cyclone pyrolysis pilot plant to enable separation of the produced pyrolysis vapors into five oil fractions. The sampling system was composed of cyclonic condensers and coalescing filters arranged in series. The objective was to characterize the oil fractions produced from three different Nordic feedstocks and suggest possible applications. The oil fractions were thoroughly characterized using several analytical techniques including water content; elemental composition; heating value, and chemical compound group analysis using solvent fractionation, quantitative 13C NMR and 1H NMR and GC x GC − TOFMS. The results show that the oil fractions significantly differ from each other both in chemical and physical properties. The first fractions and the fraction composed of aerosols were highly viscous and contained larger energy-rich compounds of mainly lignin-derived material. The middle fraction contained medium-size compounds with relatively high concentration of water, sugars, alcohols, hydrocarbonyls and acids and finally the last fraction contained smaller molecules such as water, aldehydes, ketones and acids. However, the properties of the respective fractions seem independent on the studied feedstock types, i.e. the respective fractions produced from different feedstock are rather similar. This promotes the possibility to vary the feedstock depending on availability while retaining the oil properties. Possible applications of the five fractions vary from oil for combustion and extraction of the pyrolytic lignin in the early fractions to extraction of sugars from the early and middle fractions, and extraction of acids and aldehydes in the later fractions.
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| 8. |
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| 9. |
- Leijenhorst, Evert J., et al.
(författare)
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Entrained flow gasification of straw- and wood-derived pyrolysis oil in a pressurized oxygen blown gasifier
- 2015
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Ingår i: Biomass and Bioenergy. - : Elsevier BV. - 0961-9534 .- 1873-2909. ; 79, s. 166-176
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Tidskriftsartikel (refereegranskat)abstract
- Fast pyrolysis oil can be used as a feedstock for syngas production. This approach can have certain advantages over direct biomass gasification. Pilot scale tests were performed to investigate the route from biomass via fast pyrolysis and entrained flow gasification to syngas. Wheat straw and clean pine wood were used as feedstocks; both were converted into homogeneous pyrolysis oils with very similar properties using in-situ water removal. These pyrolysis oils were subsequently gasified in a pressurized, oxygen blown entrained flow gasifier using a thermal load of 0.4 MW. At a pressure of 0.4 MPa and a lambda value of 0.4, temperatures around 1250 °C were obtained. Syngas volume fractions of 46% CO, 30% H2 and 23% CO2 were obtained for both pyrolysis oils. 2% of CH4 remained in the product gas, along with 0.1% of both C2H2 and C2H4. Minor quantities of H2S (3 vs. 23) cm3 m−3, COS (22 vs. 94) cm3 m−3 and benzene (310 vs. 532) cm3 m−3 were measured for wood- and straw derived pyrolysis oils respectively. A continuous 2-day gasification run with wood derived pyrolysis oil demonstrated full steady state operation. The experimental results show that pyrolysis oils from different biomass feedstocks can be processed in the same gasifier, and issues with ash composition and melting behaviour of the feedstocks are avoided by applying fast pyrolysis pre-treatment.
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| 10. |
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