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  • 1.
    Bergvall, Niklas
    et al.
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Cheah, You Wayne
    Chalmers University of Technology, Sweden.
    Bernlind, Christian
    RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.
    Bernlind, Alexandra
    RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.
    Olsson, Louise
    Chalmers University of Technology, Sweden.
    Creaser, Derek
    Chalmers University of Technology, Sweden.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Öhrman, Olov GW
    Preem AB, Sweden.
    Upgrading of fast pyrolysis bio-oils to renewable hydrocarbons using slurry- and fixed bed hydroprocessing2024In: Fuel processing technology, ISSN 0378-3820, E-ISSN 1873-7188, Vol. 253, article id 108009Article in journal (Refereed)
    Abstract [en]

    Liquefaction of lignocellulosic biomass through fast pyrolysis, to yield fast pyrolysis bio-oil (FPBO), is a technique that has been extensively researched in the quest for finding alternatives to fossil feedstocks to produce fuels, chemicals, etc. Properties such as high oxygen content, acidity, and poor storage stability greatly limit the direct use of this bio-oil. Furthermore, high coking tendencies make upgrading of the FPBO by hydrodeoxygenation in fixed-bed bed hydrotreaters challenging due to plugging and catalyst deactivation. This study investigates a novel two-step hydroprocessing concept; a continuous slurry-based process using a dispersed NiMo-catalyst, followed by a fixed bed process using a supported NiMo-catalyst. The oil product from the slurry-process, having a reduced oxygen content (15 wt%) compared to the FPBO and a comparatively low coking tendency (TGA residue of 1.4 wt%), was successfully processed in the downstream fixed bed process for 58 h without any noticeable decrease in catalyst activity, or increase in pressure drop. The overall process resulted in a 29 wt% yield of deoxygenated oil product (0.5 wt% oxygen) from FPBO with an overall carbon recovery of 68%.

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  • 2.
    Bergvall, Niklas
    et al.
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Molinder, Roger
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Johansson, Ann-Christine
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Continuous Slurry Hydrocracking of Biobased Fast Pyrolysis Oil2021In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 35, no 3, p. 2303-2312Article in journal (Refereed)
    Abstract [en]

    Co-refining of fast pyrolysis bio-oil together with fossil oil in existing refinery infrastructure is an attractive and cost-efficient route to conversion of lignocellulosic biomass to transportation fuel. However, due to large differences in properties between the two oils, special notice is needed to reduce process-related issues. Here, fast pyrolysis bio-oil produced from lignocellulosic biomass was co-refined with vacuum gas oil at a 20:80 weight ratio in continuous operation in a pilot-scale slurry hydrocracker in order to investigate the impact of process parameters on product quality and process performance. Mass balances together with product characterization were used to investigate product yields, product composition, and hydrodeoxygenation. Best conversion and hydrodeoxygenation of the fast pyrolysis bio-oil was achieved using an unsupported catalyst loading of 900 ppm Mo with either a low temperature (410 °C) and long residence time (2 h) or higher temperature (435 °C) and shorter residence time (1 h). These settings resulted in about 94% hydrodeoxygenation but also led to highest yield of biogenic carbon to gas phase (40-43 wt %) and lowest yield of biogenic carbon to oil fractions (53-56 wt %) as well as the water fraction (3-5 wt %). Successfully, coke yield remained low at around 0.07-0.10 wt % for all performed runs, which was comparable to the insoluble particle content in the feed due to the presence of particles in the untreated fast pyrolysis bio-oil. Co-processing pyrolysis oil with fossil oil in a slurry hydrocracker seems to be a robust process with regard to coke formation, which should lead to reduced plugging issues compared to fixed bed hydrotreaters. Although this study gives a brief understanding of the effect of process parameters on the processing of fast pyrolysis bio-oil, further research is required to find optimal process parameters and to fully comprehend the possibilities and limitations for production of transportation fuels from fast pyrolysis bio-oil using this technology.

  • 3.
    Bergvall, Niklas
    et al.
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Cheah, Y. W.
    Chalmers University of Technology, Sweden.
    Öhrman, Olov
    Preem Ab, Sweden.
    Slurry Hydroconversion of Solid Kraft Lignin to Liquid Products Using Molybdenum- and Iron-Based Catalysts2022In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 36, no 17, p. 10226-Article in journal (Refereed)
    Abstract [en]

    Kraft lignin is an abundantly available and largely underutilized renewable material with potential for production of biobased fuels and chemicals. This study reports the results of a series of slurry hydroprocessing experiments with the aim of converting solid Kraft lignin to liquid products suitable for downstream refining in more conventional reactors. Experiments reported in this study were conducted by feeding a lignin slurry to an already hot, liquid-filled reactor to provide momentaneous heating of the lignin to the reaction temperature. This modified batch procedure provided superior results compared to the regular batch experiments, likely since unwanted repolymerization and condensation reactions of the lignin during the heating phase was avoided, and was therefore used for most of the experiments reported. Experiments were performed using both an unsupported Mo-sulfide catalyst and Fe-based catalysts (bauxite and hematite) at varied reaction temperatures, pressures, and catalyst loadings. The use of Mo-sulfide (0.1% Mo of the entire feed mass) at 425 °C and 50 bar resulted in complete conversion of the Kraft lignin to nonsolid products. Very high conversions (>95%) could also be achieved with both sulfided bauxite or hematite at the same temperature and pressure, but this required much higher catalyst loadings (6.25% bauxite or 4.3% hematite of the total feed mass), and around 99% conversion could be achieved at higher temperatures but at the expense of much higher gas yields. Although requiring much higher loadings, the results in this study suggest that comparatively nonexpensive Fe-based catalysts may be an attractive alternative for a slurry-based process aimed at the hydroconversion of solid lignin to liquid products. Possible implementation strategies for a slurry-based hydroconversion process are proposed and discussed. © 2022 The Authors.

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  • 4.
    Bergvall, Niklas
    et al.
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Weiland, Fredrik
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Öhrman, Olov G. W.
    Preem AB, Sweden.
    Corefining of Fast Pyrolysis Bio-Oil with Vacuum Residue and Vacuum Gas Oil in a Continuous Slurry Hydrocracking Process2020In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 34, no 7, p. 8452-8465Article in journal (Refereed)
    Abstract [en]

    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.

  • 5.
    Bulsink, Philip
    et al.
    Natural Resources Canada, Canada.
    De Miguel Mercader, Ferran
    Scion, New Zealand.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Van De Beld, Bert
    BTG Biomass Technology Group BV, Netherlands.
    Preto, Fernando
    Natural Resources Canada, Canada.
    Zacher, Alan H.
    Pacific Northwest National Laboratory, USA.
    Oasmaa, Anja
    VTT Technical Research Centre of Finland, Finland.
    Dahmen, Nicolaus
    Karlsruhe Institute of Technology, Germany.
    Funke, Axel
    Karlsruhe Institute of Technology, Germany.
    Bronson, Benjamin
    Natural Resources Canada, Canada.
    Results of the International Energy Agency Bioenergy Round Robin on the Analysis of Heteroatoms in Biomass Liquefaction Oils2020In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 34, no 9Article in journal (Refereed)
    Abstract [en]

    A round robin study evaluating the analysis of biomass liquefaction oils (BLOs) from fast pyrolysis and hydrothermal liquefaction (HTL) was performed, receiving data from 14 laboratories in seven countries in order to assess the current status of analytical techniques for the determination of nitrogen, sulfur, and chlorine content in BLOs and to evaluate potential differences in origin (i.e., fast pyrolysis versus HTL). The BLOs were produced from a range of feedstocks including pine, mixed softwoods, forest residues, microalgae, miscanthus, and wheat straw to cover a variety in nitrogen, sulfur, and chlorine content and speciation. Nine samples were distributed, comprised of eight separate BLOs and one blind duplicate produced by five producers. The samples were analyzed for water, carbon, hydrogen, nitrogen, sulfur, and chlorine content. No analytical test method was mandated; laboratories were encouraged to utilize whichever method they determined would be most applicable, relying on the existing body of BLO literature as a guide. The results of this round robin study are presented in this paper. The results of the carbon, hydrogen, and water measurements as reference analyses had relative standard deviations (2.9, 3.5, and 5.6%, respectively) that were comparable to those found in past round robin studies on fast pyrolysis bio-oil. The analysis of nitrogen, sulfur, and chlorine showed higher levels of variability. Laboratories mostly chose the same method for water, carbon, hydrogen, and nitrogen determination, whereas there were a variety of methods chosen for sulfur and chlorine determination. The results suggest that specific analytical methods for the determination of nitrogen, sulfur, and chlorine should be further refined to ensure reproducible and accurate results for BLO analysis due to their importance in emissions, material selection, and catalyst activity.

  • 6.
    Dimitriadis, Athanasios
    et al.
    CPERI & CERTH, Greece.
    Bergvall, Niklas
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Johansson, Ann-Christine
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Bezergianni, Stella
    CPERI & CERTH, Greece.
    Tourlakidis, Nikos
    CPERI & CERTH, Greece.
    Meca, Ludek
    Ranido sro, Czech Republic.
    Kukula, Pavel
    Ranido sro, Czech Republic.
    Raymakers, Leonard
    HyET Hydrogen BV, Netherlands.
    Biomass conversion via ablative fast pyrolysis and hydroprocessing towards refinery integration: Industrially relevant scale validation2023In: Fuel, ISSN 0016-2361, E-ISSN 1873-7153, Vol. 332, article id 126153Article in journal (Refereed)
    Abstract [en]

    Reducing the use of fossil fuels is an ongoing and important effort considering the environmental impact and depletion of fossil-based resources. The combination of ablative fast pyrolysis and hydroprocessing is explored as a pathway allowing bio-based intermediates (BioMates) integration in underlying petroleum refineries. The proposed technology is validated in industrially relevant scale, identifying pros and cons towards its commercialization. Straw from wheat, rye and barley was fed to ablative fast pyrolysis rendering Fast Pyrolysis Bio-Oil (FPBO) as the main product. The FPBO was stabilized via slurry hydroprocessing, rendering a stabilized FPBO (sFPBO) with 49 % reduced oxygen content, 71 % reduced carbonyl content and 49 % reduced Conradson carbon residue. Fixed bed catalytic hydroprocessing of sFPBO resulted in the production of BioMates, a high bio-content product to be co-fed in established refinery units. Compared to the starting biomass, BioMates has 83.6 wt% C content increase, 92.5 wt% O content decrease, 93.0 wt% water content decrease, while the overall technology has 20 wt% conversion yield (32 wt% carbon yield) from biomass to BioMates. © 2022 The Author(s)

  • 7.
    Johansson, Ann-Christine
    et al.
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Bergvall, Niklas
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Molinder, Roger
    RISE Research Institutes of Sweden.
    Wikberg, Elena
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Niinipuu, Mirva
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Comparison of co-refining of fast pyrolysis oil from Salix via catalytic cracking and hydroprocessing2023In: Biomass and Bioenergy, ISSN 0961-9534, E-ISSN 1873-2909, Vol. 172, article id 106753Article in journal (Refereed)
    Abstract [en]

    Lignocellulosic biomass from energy crops, i.e., short rotation coppice willows such as Salix spp., can be used as feedstock for production of transportation biofuels. Biomass conversion via fast pyrolysis followed by co-refining with fossil oil in existing refinery infrastructure could enable a fast introduction of large-scale production of biofuels. In this study, Salix was first liquefied using ablative fast pyrolysis in a pilot scale unit. The resulting pyrolysis oil, rich in oxygenates, was thereafter co-refined in 20 wt% ratio with fossil feedstock using two separate technologies, a fluidized catalytic cracking (FCC) laboratory unit and a continuous slurry hydroprocessing pilot plant. In the FCC route, the pyrolysis oil was cracked at 798 K using a commercial FCC catalyst at atmospheric pressure, while in the hydroprocessing route, the oil was processed at 693 K and a hydrogen pressure of 15 MPa in the presence of an unsupported molybdenum sulfide catalyst. Both routes resulted in significant deoxygenation (97 wt% versus 93 wt%). It is feasible to co-refine pyrolysis oil using both methods, the main difference being that the hydroprocessing results in a significantly higher biogenic carbon yield from the pyrolysis oil to liquid and gaseous hydrocarbon products (92 wt%) but would in turn require input of H2. In the cracking route, besides the liquid product, a significant part of the biogenic carbon ends up as gas and as coke on the catalyst. The choice of route depends, among other factors, on the available amount of bio-oil and refining infrastructures. © 2023 The Authors

  • 8.
    Johansson, Ann-Christine
    et al.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Iisa, Kristiina
    National Renewable Energy Laboratory, USA.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Ben, Haoxi
    National Renewable Energy Laboratory, USA.
    Pilath, Heidi
    National Renewable Energy Laboratory, USA.
    Deutch, Steve
    National Renewable Energy Laboratory, USA.
    Wiinikka, Henrik
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Öhrman, Olov G.W.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Fractional condensation of pyrolysis vapors produced from Nordic feedstocks in cyclone pyrolysis2017In: Journal of Analytical and Applied Pyrolysis, ISSN 0165-2370, E-ISSN 1873-250X, Vol. 123, p. 244-254Article in journal (Refereed)
    Abstract [en]

    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.

  • 9.
    Johansson, Ann-Christine
    et al.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Wiinikka, Henrik
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Öhrman, Olov G.W.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Experiences of pilot scale cyclone pyrolysis2017In: European Biomass Conf. Exhib. Proc., ETA-Florence Renewable Energies , 2017, no 25thEUBCE, p. 952-955Conference paper (Refereed)
    Abstract [en]

    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. 

  • 10.
    Johansson, Ann-Christine
    et al.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Öhrman, Olov
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center. Luleå University of Technology, Sweden.
    Jilvero, Henrik
    Stena Metall, Sweden.
    Co-pyrolysis of woody biomass and plastic waste in both analytical and pilot scale2018In: Journal of Analytical and Applied Pyrolysis, ISSN 0165-2370, E-ISSN 1873-250X, Vol. 134, p. 102-1113Article in journal (Refereed)
    Abstract [en]

    Earlier studies show that co-pyrolysis of biomass and plastics can improve the quantity and quality of the produced pyrolysis oil compared to pyrolysis of the separate feedstocks. In this work three relevant plastic wastes; paper reject, shredder light fraction and cable plastics; were evaluated together with woody biomass (stem wood from spruce and pine) using analytical pyrolysis, Py-GC–MS/FID. One verification experiment was also conducted in a cyclone pyrolyser pilot plant at industrially relevant conditions. The addition of plastic waste to woody biomass pyrolysis was found to significantly affect the composition and properties of the produced pyrolysis products. In analytical pyrolysis experiments, positive synergetic effects were observed in the co-pyrolysis of paper reject and cable plastics together with the stem wood. The yield of reactive oxygenated compounds (ketones, aldehydes and acids) was suppressed while more stable alcohols and esters were promoted. The formation of hydrocarbons was also promoted in the co-pyrolysis of plastics from paper reject and stem wood. The results from the analytical pyrolysis were partly verified in the pilot scale experiment by co-pyrolysing stem wood and paper reject. However, the co-pyrolysis also affected other parameters that cannot be detected in analytical pyrolysis such as higher acidity and viscosity of the oil which highlights the need for undertaking experiments at different scales. The product yields in pilot scale were about the same for the co-pyrolysis case as for pure stem wood. However, a high volatile content of the solid product indicated that the process conditions can be further optimized for co-pyrolysing cases.

  • 11.
    Johansson, Ann-Christine
    et al.
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Wiinikka, Henrik
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Sandström, Linda
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Marklund, Magnus
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Öhrman, Olov G. W.
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Narvesjö, Jimmy
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Characterization of pyrolysis products produced from different Nordic biomass types in a cyclone pilot plant2016In: Fuel processing technology, ISSN 0378-3820, E-ISSN 1873-7188, Vol. 146, p. 9-19Article in journal (Refereed)
    Abstract [en]

    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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  • 12.
    Lestander, Torbjörn A.
    et al.
    SLU Swedish University of Agricultural Sciences, Sweden.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Wiinikka, Henrik
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Öhrman, Olov
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Thyrel, Mikael
    SLU Swedish University of Agricultural Sciences, Sweden.
    Characterization of fast pyrolysis bio-oil properties by near-infrared spectroscopic data2018In: Journal of Analytical and Applied Pyrolysis, ISSN 0165-2370, E-ISSN 1873-250X, Vol. 133, p. 9-15Article in journal (Refereed)
    Abstract [en]

    Pyrolysis transforms bulky and heterogeneous lignocellulosic biomass into more easily-handled oils that can be upgraded into bio-based transportation fuels. Existing systems for monitoring pyrolysis processes and characterizing their products rely on slow and time-consuming wet chemical analyses. On-line near-infrared (NIR) spectroscopy could potentially replace such analyses, providing real-time data and reducing costs. To test the usefulness of NIR methods in characterizing pyrolysis oils and processes, biomass from conifers, Salix, and reed canary grass was milled and pyrolyzed at 675, 750, and 775 °C. Two separate pyrolytic fractions (aerosol and condensed) were produced in each experiment, and NIR spectra were collected for each fraction. Multivariate modelling of the resulting data clearly showed that the samples’ NIR spectra could be used to accurately predict important properties of the pyrolysis oils such as their energy values, main organic element (C, H and O) contents, and water content. The spectra also contained predictive information on the samples’ origins, fraction, and temperature treatment, demonstrating the potential of on-line NIR techniques for monitoring pyrolytic production processes and characterizing important properties of pyrolytic oils from lignocellulosic biomass.

  • 13.
    Molinder, Roger
    et al.
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Sandström, Linda
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Wiinikka, Henrik
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Characteristics of Particles in Pyrolysis Oil2016In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 30, no 11, p. 9456-9462Article in journal (Refereed)
    Abstract [en]

    Particles filtered out of pyrolysis oil produced through fast pyrolysis of stem wood, willow, reed canary grass, bark, and forest residue were characterized using scanning electron microscopy and energy-dispersive spectroscopy with the aim of identifying particle categories and discussing transport mechanisms of particles and inorganics into the oil. Particles filtered out of both the condensed and the aerosol fractions of the oil displayed three types of morphology: (i) char-like structures (1-15 μm), (ii) spheres (100 nm to 1 μm), and (iii) irregularly shaped residue (50-500 nm). The char-like structures were identified as char. The spheres and irregularly shaped residue shared morphology and composition with tar balls and organic particles with inorganic inclusions. These particles could have formed either during the fast pyrolysis stage or through precipitation from the oil during storage. All particles consisted mainly of C and O but also small amounts of inorganics. The particles from the aerosol fraction of the oil had higher inorganics content than the particles from the condensed fraction. The results were discussed, and suggested transport mechanisms of inorganics into particles were presented.

  • 14.
    Pedersen, Thomas Helmer
    et al.
    Aalborg University, Denmark.
    Jensen, Claus Uhrenholt
    Steeper Energy ApS, Denmark.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Rosendahl, Lasse Aistrup
    Aalborg University, Denmark.
    Full characterization of compounds obtained from fractional distillation and upgrading of a HTL biocrude2017In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 202, p. 408-419Article in journal (Refereed)
    Abstract [en]

    Biocrude from hydrothermal liquefaction of biomass provides a sustainable source from which to produce chemicals and fuels. However, just as for fossil crude, the chemical complexity of the biocrude impedes the characterization and hence identification of market potentials for both biocrude and individual fractions. Here, we reveal how fractional distillation of a biocrude can leverage biocrude characterization beyond state-of-the-art and uncover the full biocrude potential. By distillation combined with detailed individual analysis of the distillate fractions and distillation residue, more than 85% of the total biocrude composition is determined. It is demonstrated that a total mass fraction of 48.2% of the biocrude is volatile below 350 °C, comprising mainly value-added marketable ketones, oxygenated aromatics and prospective liquid fuel candidates, which are easily fractionated according to boiling points. Novel, high resolution pyr-GCxGC-MS analysis of the residue indicates a high molecular weight aromatic structure, valuable for bio-materials production or for further processing into fuels. The distillate fractions are mildly hydrotreated to show the fuel and chemical precursor potential of the volatile components. This results in the formation of mainly hydrocarbons and added-value phenolics. This work takes a significant step by going beyond the biocrude as an intermediate bulk energy product and addressing actual applications and pathways to these.

  • 15.
    Persson, H.
    et al.
    KTH Royal Institute of Technology, Sweden.
    Han, T.
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE - Research Institutes of Sweden (2017-2019), Bioeconomy, ETC Energy Technology Center.
    Xia, W.
    KTH Royal Institute of Technology, Sweden.
    Evangelopoulos, Panagiotis
    KTH Royal Institute of Technology, Sweden.
    Yang, W.
    KTH Royal Institute of Technology, Sweden.
    Fractionation of liquid products from pyrolysis of lignocellulosic biomass by stepwise thermal treatment2018In: Energy, ISSN 0360-5442, E-ISSN 1873-6785, Vol. 154, p. 346-351Article in journal (Refereed)
    Abstract [en]

    The thermal properties of cellulose, hemicellulose and lignin can be utilized to improve the characteristics of pyrolysis liquids. In this study, a concept of stepwise pyrolysis to fractionate the liquid based on the thermal properties of the biomass constituents was investigated. Lignocellulosic biomass was thermally treated in two steps: 200–300 °C followed by 550 °C. Derived liquids were studied for GC/MS analysis, water content, acid concentration and a solvent extraction method. Pyrolytic liquid derived from 550 °C after treatment at lower temperatures have a higher relative composition of phenolic compounds compared to one-step pyrolysis (increased from 58 to 90% of GC/MS peak area). Also, compounds known to promote aging, such as acids and carbonyl compounds, are derived at lower temperatures which may suppress aging in the liquid derived downstream at 550 °C. For liquids derived at 550 °C, the total acid number was reduced from 125 in one-step treatment to 14 in two-step treatment. Overall, no significant difference in the total liquid yield (sum of the liquids derived in separated treatments) nor any variations in their collective composition compared to one-step treatment at 550 °C was observed, i.e. stepwise pyrolysis can be utilized for direct fractionation of pyrolytic vapors.

  • 16.
    Sandström, Linda
    et al.
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Johansson, Ann-Christine
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Wiinikka, Henrik
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Öhrman, Olov G. W.
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Marklund, Magnus
    RISE, SP – Sveriges Tekniska Forskningsinstitut, SP Energy Technology Center.
    Pyrolysis of Nordic biomass types in a cyclone pilot plant — Mass balances and yields2016In: Fuel processing technology, ISSN 0378-3820, E-ISSN 1873-7188, Vol. 152, p. 274-284Article in journal (Refereed)
    Abstract [en]

    Fast pyrolysis of biomass results in a renewable product usually denoted pyrolysis oil or bio-oil, which has been suggested to be used as a direct substitute for fuel oil or as a feedstock for production of transportation fuels and/or chemicals. In the present work, fast pyrolysis of stem wood (originated from pine and spruce), willow, reed canary grass, brown forest residue and bark has been performed in a pilot scale cyclone reactor. The experiments were based on a biomass feeding rate of 20 kg/h at three different reactor temperatures. At the reference condition, pyrolysis of stem wood, willow, reed canary grass, and forest residue resulted in organic liquid yields in the range of 41 to 45% w/w, while pyrolysis of bark resulted in lower organic liquid yields. Two fractions of pyrolysis oil were obtained, denoted as the condensed and the aerosol fraction. Most of the water soluble molecules were collected in the condensed fraction, whereas the yield of water insoluble, heavy lignin molecules was higher in the aerosol fraction. Based on the results of the present work, willow, reed canary grass and forest residue are considered as promising raw materials for production of pyrolysis oil in a cyclone reactor.

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  • 17.
    Shafaghat, Hoda
    et al.
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Linderberg, Mats
    RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.
    Janosik, Tomasz
    RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.
    Hedberg, Martin
    RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.
    Wiinikka, Henrik
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Johansson, Ann-Christine
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Enhanced Biofuel Production via Catalytic Hydropyrolysis and Hydro-Coprocessing2022In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 36, no 1, p. 450-462Article in journal (Refereed)
    Abstract [en]

    In order to successfully integrate biomass pyrolysis oils as starting materials for conventional oil refineries, upgrading of the pyrolysis oils is needed to achieve desired properties, something which can be performed either as part of the pyrolysis process and/or by separate catalytic treatment of the pyrolysis intermediate oil products. In this study, the quality of stem wood-derived pyrolysis oil was improved via ex situ catalytic hydropyrolysis in a bench-scale pyrolyzer (stage 1), followed by catalytic hydro-coprocessing with fossil co-feed in a laboratory-scale high pressure autoclave (stage 2). The effect of pyrolysis upgrading conditions was investigated based on the quality of intermediate products and their suitability for hydro-coprocessing. HZSM-5 and Pt/TiO2 catalysts (400 °C, atmospheric pressure) were employed for ex situ pyrolysis, and the NiMoS/Al2O3 catalyst (330 °C, 100 bar H2 initial pressure) was used for hydro-coprocessing of the pyrolysis oil. The application of HZSM-5 in the pyrolysis of stem wood under a N2 atmosphere decreased the formation of acids, ketones, aldehydes, and furans and increased the production of aromatic hydrocarbons and phenolics (guaiacols and phenols). Replacing HZSM-5 with Pt/TiO2 and N2 with H2 resulted in complete conversion of guaiacols and significant production of phenols, with further indications of increased stability and reduced coking tendencies.

  • 18.
    Sophonrat, Nanta
    et al.
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Johansson, Ann-Christine
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    Co-pyrolysis of Mixed Plastics and Cellulose: An Interaction Study by Py-GC×GC/MS2017In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 31, no 10, p. 11078-11090Article in journal (Refereed)
    Abstract [en]

    Understanding of the interaction between cellulose and various plastics is crucial for designing waste-to-energy processes. In this work, co-pyrolysis of polystyrene (PS) and cellulose was performed in a Py-GC×GC/MS system at 450-600 °C with ratios 70:30, 50:50, and 30:70. Polypropylene (PP), polyethylene (PE), and polyethylene terephthalate (PET) were then added to the mixture with different ratios. It was found that co-pyrolysis of PS and cellulose promotes the formation of aromatic products with a large increase in the yield of ethylbenzene as compared to the calculated value from individual feedstock. This indicates interactions between cellulose and PS pyrolysis products. Observations from experiments including more than one type of plastics indicate that the interactions between different plastics are more pronounced than the interaction between plastics and cellulose.

  • 19.
    Sophonrat, Nanta
    et al.
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Svanberg, Rikard
    KTH Royal Institute of Technology, Sweden.
    Han, Tong
    KTH Royal Institute of Technology, Sweden.
    Dvinskikh, Sergey
    KTH Royal Institute of Technology, Sweden.
    Lousada, Claudio
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    Ex Situ Catalytic Pyrolysis of a Mixture of Polyvinyl Chloride and Cellulose Using Calcium Oxide for HCl Adsorption and Catalytic Reforming of the Pyrolysis Products2019In: Industrial & Engineering Chemistry Research, ISSN 0888-5885, E-ISSN 1520-5045, Vol. 58, no 31, p. 13960-13970Article in journal (Refereed)
    Abstract [en]

    In the context of chemical recycling of mixed plastics and paper, multitemperature step pyrolysis has shown good potential for the separation of oxygenated products from hydrocarbons. Here, we report results of an investigation of the first pyrolysis step at low temperature, which involves the dehydrochlorination of polyvinyl chloride (PVC) and the pyrolysis of cellulose, the main component of paper. Calcium oxide (CaO), selected for its chloride adsorption ability and its catalytic activity on biooil deoxygenation, was used for upgrading the downstream products from the pyrolysis. Additionally, we studied the performance of CaO for the simultaneous adsorption of HCl and for reforming cellulose pyrolysates in the temperature range of 300-600 °C with feedstock to CaO ratios of 1:0.2, 1:0.4, and 1:1. It was found that the suitable catalytic temperature for HCl and acetic acid adsorption is lower than 400 °C. This is due to the desorption of HCl from CaCl2 and Ca(OH)Cl in the presence of water and CO2 at 400 °C and higher. A larger amount of CaO resulted in a more efficient reduction of acids and the organic liquids were found to have lower amounts of oxygen. A comparison between the cases of neat and mixed feedstock showed that pyrolysis of mixed feedstock produced more water, H2, CO, and polycyclic aromatic hydrocarbons (PAHs) when compared to the case of neat materials over CaO

  • 20.
    Sophonrat, Nanta
    et al.
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Zaini, Ilman N.
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    Stepwise pyrolysis of mixed plastics and paper for separation of oxygenated and hydrocarbon condensates2018In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 229, p. 314-325Article in journal (Refereed)
    Abstract [en]

    Mixed plastics and papers are two of the main fractions in municipal solid waste which is a critical environmental issue today. Recovering energy and chemicals from this waste stream by pyrolysis is one of the favorable options to achieve a circular economy. While pyrolysis products from plastics are mainly hydrocarbons, pyrolysis products from paper/biomass are highly oxygenated. The different nature of the two pyrolysis products results in different treatments and applications as well as economic values. Therefore, separation of these two products by multi-step pyrolysis based on their different decomposition temperatures could be beneficial for downstream processes to recover materials, chemicals and/or energy. In this work, stepwise pyrolysis of mixed plastics and paper waste was performed in a batch type fixed bed reactor using two different pyrolysis temperatures. Neat plastic materials (polystyrene, polyethylene) and cellulose mixtures were used as starting materials. Then, the same conditions were applied to a mixed plastics and paper residue stream derived from paper recycling process. The condensable products were analyzed by GC/MS. It was found that pyrolysis temperatures during the first and second step of 350 and 500 °C resulted in a better separation of the oxygenated and hydrocarbon condensates than when a lower pyrolysis temperature (300 °C) was used in the first step. The products from the first step were derived from cellulose with some heavy fraction of styrene oligomers, while the products from the second step were mainly hydrocarbons derived from polystyrene and polyethylene. This thus shows that stepwise pyrolysis can separate the products from these materials, although with some degree of overlapping products. Indications of interaction between PS and cellulose during stepwise pyrolysis were observed including an increase in char yield, a decrease in liquid yield from the first temperature step and changes in liquid composition, compared to stepwise pyrolysis of the two materials separately. A longer vapor residence time in the second step was found to help reducing the amount of wax derived from polyethylene. Results from stepwise pyrolysis of a real waste showed that oxygenated and acidic products were concentrated in the liquid from the first step, while the product from the second step contained a high portion of hydrocarbons and had a low acid number.

  • 21.
    Wiinikka, Henrik
    et al.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Johansson, Ann-Christine
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Öhrman, Olov G.W.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Fate of inorganic elements during fast pyrolysis of biomass in a cyclone reactor2017In: Fuel, ISSN 0016-2361, E-ISSN 1873-7153, Vol. 203, p. 537-547Article in journal (Refereed)
    Abstract [en]

    In order to reduce ash related operational problem and particle emissions during pyrolysis oil combustion it is important to produce pyrolysis oil with very low concentration of inorganics. In this paper, the distribution of all major inorganic elements (S, Si, Al, Ca, Fe, K, Mg, Mn, Na, P, Ti and Zn) in the pyrolysis products (solid residue and two fractions of pyrolysis oil) was investigated during pyrolysis of stem wood, bark, forest residue, salix and reed canary grass. The raw materials were pyrolysed in a cyclone reactor and the produced pyrolysis oils were recovered as two oil fractions, a condensed fraction and an aerosol fraction. The inorganic composition of the ingoing raw material, the solid residue and the two pyrolysis oil fractions were analysed with inductively coupled plasma spectrometry techniques. All major inorganic elements, except sulphur, were concentrated in the solid residue. A significant amount of sulphur was released to the gas phase during pyrolysis. For zinc, potassium and iron about 1–10 wt% of the ingoing amount, depending on the raw material, was found in the pyrolysis oil. For the rest of the inorganics, generally less than 1 wt% of the ingoing amount was found in the pyrolysis oil. There were also differences in distribution of inorganics between the condensed and the aerosol oil fractions. The easily volatilized inorganic elements such as sulphur and potassium were found to a larger extent in the aerosol fraction, whereas the refractory elements were found to a larger extent in the condensed fraction. This implies that oil fractionation can be a method to produce oil fractions with different inorganic concentrations which thereafter can be used in different technical applications depending on their demand on the inorganic composition of the pyrolysis oil.

  • 22.
    Winikka, Henrik
    et al.
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center. Luleå University of Technology, Sweden.
    Toth, Pal
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center. University of Miskolc, Hungary.
    Jansson, Kjell
    Stockholm University, Sweden.
    Molinder, Roger
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Broström, Markus
    Umeå University, Sweden.
    Sandström, Linda
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Lighty, JoAnn S.
    University of Utah, USA.
    Weiland, Fredrik
    RISE - Research Institutes of Sweden, Bioeconomy, ETC Energy Technology Center.
    Particle formation during pressurized entrained flow gasification of wood powder: Effects of process conditions on chemical composition, nanostructure, and reactivity2018In: Combustion and Flame, ISSN 0010-2180, E-ISSN 1556-2921, Vol. 189, p. 1339-1351Article in journal (Refereed)
    Abstract [en]

    The influence of operating condition on particle formation during pressurized, oxygen blown gasification of wood powder with an ash content of 0.4 wt% was investigated. The investigation was performed with a pilot scale gasifier operated at 7 bar(a). Two loads, 400 and 600 kW were tested, with the oxygen equivalence ratio (λ) varied between 0.25 and 0.50. Particle concentration and mass size distribution was analyzed with a low pressure cascade impactor and the collected particles were characterized for morphology, elemental composition, nanostructure, and reactivity using scanning electron microscopy/high resolution transmission electron microscopy/energy dispersive spectroscopy, and thermogravimetric analysis. In order to quantify the nanostructure of the particles and identify prevalent sub-structures, a novel image analysis framework was used. It was found that the process temperature, affected both by λ and the load of the gasifier, had a significant influence on the particle formation processes. At low temperature (1060 °C), the formed soot particles seemed to be resistant to the oxidation process; however, when the oxidation process started at 1119 °C, the internal burning of the more reactive particle core began. A further increase in temperature (> 1313 °C) lead to the oxidation of the less reactive particle shell. When the shell finally collapsed due to severe oxidation, the original soot particle shape and nanostructure also disappeared and the resulting particle could not be considered as a soot anymore. Instead, the particle shape and nanostructure at the highest temperatures (> 1430 °C) were a function of the inorganic content and of the inorganic elements the individual particle consisted of. All of these effects together lead to the soot particles in the real gasifier environment having less and less ordered nanostructure and higher and higher reactivity as the temperature increased; i.e., they followed the opposite trend of what is observed during laboratory-scale studies with fuels not containing any ash-forming elements and where the temperature was not controlled by λ.

  • 23.
    Yang, Hanmin
    et al.
    KTH Royal Institute of Technology, Sweden.
    Cui, Yuxiao
    KTH Royal Institute of Technology, Sweden.
    Han, Tong
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Jönsson, Pär
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    High-purity syngas production by cascaded catalytic reforming of biomass pyrolysis vapors2022In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 322, article id 119501Article in journal (Refereed)
    Abstract [en]

    A novel pyrolysis followed by in-line cascaded catalytic reforming process without additional steam was developed to produce high-purity syngas from woody biomass. The key to the proposed process is the construction of a cascaded biochar + NiAl2O4 catalytic reforming process in which biochar acts as a pre-reforming catalyst, and NiAl2O4 acts as a primary reforming catalyst. The large oxygenates in the pyro-vapors are deeply cracked in the biochar layer due to the increased residence time in the hot-biochar bed. The remaining small molecules are then reformed with the autogenerated steam from pyrolysis catalyzed by the reduced Ni0 species in the NiAl2O4 catalyst (NiAlO). The results showed that the yield of syngas for the optimized process was 71.28 wt% (including 44.44 mg-H2/g-biomass and 536.48 mg-CO/g-biomass), and the CO2 yield of the process was only 3 kg-CO2/kg-hydrogen. High-purity syngas with 89.47 vol% of (H2 + CO) was obtained, and the gas energy conversion efficiency (GECE) of the process reached 75.65%. The study shows that in the cascaded catalytic reforming process, cracking of the large oxygenates and reforming of the small molecules are promoted sequentially in separated biochar + NiAlO catalyst layers, which maximizes the syngas production and improves the activity and stability of the Ni-based catalyst. © 2022 The Author(s)

  • 24.
    Yang, Hanmin
    et al.
    KTH Royal Institute of Technology, Sweden.
    Cui, Yuxiao
    KTH Royal Institute of Technology, Sweden.
    Jin, Yanghao
    KTH Royal Institute of Technology, Sweden.
    Lu, Xincheng
    Institute of Chemical Industry of Forest Products, China.
    Han, Tong
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Jönsson, Pär G
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    Evaluation of Engineered Biochar-Based Catalysts for Syngas Production in a Biomass Pyrolysis and Catalytic Reforming Process2023In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029Article in journal (Refereed)
    Abstract [en]

    Biochar, originating from biomass pyrolysis, has been proven a promising catalyst for tar cracking/reforming with great coke resistance. This work aims to evaluate various engineered biochar-based catalysts on syngas production in a biomass pyrolysis and catalytic reforming process without feeding extra steam. The tested engineered biochar catalysts include physical- and chemical-activated, nitrogen-doped, and nickel-doped biochars. The results illustrated that the syngas yields were comparable when using biochar and activated biochar as catalysts. A relatively high specific surface area (SSA) and a hierarchical porous structure are beneficial for syngas and hydrogen production. A 2 h physical-activated biochar catalyst induced the syngas with the highest H2/CO ratio (1.5). The use of N-doped biochar decreased the syngas yield sharply due to the collapse of the pore structure but obtained syngas with the highest LHVgas (18.5MJ/Nm3). The use of Ni-doped biochar facilitated high syngas and hydrogen yields (78.2 wt % and 26 mmol H2/g-biomass) and improved gas energy conversion efficiency (73%). Its stability and durability test showed a slight decrease in performance after a three-time repetitive use. A future experiment with a longer time is suggested to determine when the catalyst will finally deactivate and how to reduce the catalyst deterioration. © 2023 The Authors. 

  • 25.
    Yang, Hanmin
    et al.
    KTH Royal Institute of Technology, Sweden.
    Han, Tong
    KTH Royal Institute of Technology, Sweden.
    Shi, Ziyi
    KTH Royal Institute of Technology, Sweden.
    Sun, Yunjuan
    Institute of Chemical Industry of Forest Products, China.
    Jiang, Jianchun
    Institute of Chemical Industry of Forest Products, China.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Jönsson, Pär
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    In situ catalytic fast pyrolysis of lignin over biochar and activated carbon derived from the identical process2022In: Fuel processing technology, ISSN 0378-3820, E-ISSN 1873-7188, Vol. 227, article id 107103Article in journal (Refereed)
    Abstract [en]

    In this study, a sustainable in situ catalytic fast pyrolysis (CFP) of lignin was developed by using biochar and activated carbon (AC) as catalysts, which is derived from the same CFP of lignin process. The results showed that using biochar as the catalyst mainly promoted the production of non-condensable gas, water, and guaiacol-rich oil regardless of the biochar-to-lignin ratio. The catalytic effect of the biochar was mainly attributed to the surface sodium and alkali metals. Using AC44.7% and AC48.6% as the catalyst resulted in a high yield of guaiacol-rich oil, whereas using AC64.3% induced a great decrease of the tarry oil yield and a significant increase of the phenol concentration in bio-oil. The diffusion efficiency of the reactive intermediates inside the catalysts determined by the pore size was believed to be the greatest determinant of the catalytic performance of the ACs. The mesopores were large enough to allow most of the reactive intermediates to diffuse quickly and react. Moreover, by using the same catalyst, char agglomeration was almost completely suppressed after in situ CFP. Two major problems, tar production and char agglomeration, which limit the large-scale application of fast lignin pyrolysis are believed to be solved. © 2021 The Authors

  • 26.
    Yang, Hanmin
    et al.
    KTH Royal Institute of Technology, Sweden.
    Han, Tong
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Jönsson, Pär G
    KTH Royal Institute of Technology, Sweden.
    Influence of the porosity and acidic properties of aluminosilicate catalysts on coke formation during the catalytic pyrolysis of lignin2022In: Journal of Analytical and Applied Pyrolysis, ISSN 0165-2370, E-ISSN 1873-250X, Vol. 165, article id 105536Article in journal (Refereed)
    Abstract [en]

    Five aluminosilicate catalysts with different textural and acidic properties are used to study the influence of their acidic and porous properties on the coke formation during the fast catalytic pyrolysis of lignin. The competition between coke formation and target product (hydrocarbons) formation in regard to different pore sizes and Si/Al ratios is classified via performing X-Ray Diffraction (XRD), nitrogen adsorption-desorption, pyrolysis–gas chromatography–mass spectrometry (Py-GCMS), kinetic calculations, and thermogravimetric (TG)/temperature programmed oxidation (TPO) measurements. The results indicated that a pore size consistent with the critical diameters of the pyrolysis products of lignin is a prerequisite for a catalyst to reach a high selectivity for the desired products with less coke formation. A relatively large pore size can cause severe coke formation; however, large pores are favorable for increasing the reaction rate by increasing the diffusion efficiency. A catalyst with sufficient acidity is also essential for high selectivity towards target products. © 2022 The Authors

  • 27.
    Yang, Hanmin
    et al.
    KTH Royal Institute of Technology, Sweden.
    Nurdiawati, Anissa
    KTH Royal Institute of Technology, Sweden.
    Gond, Ritambhara
    Uppsala University, Sweden.
    Chen, Shiwei
    Shanghai Jiao Tong University, Sweden.
    Wang, Shule
    Nanjing Forestry University, China; Chinese Academy of Forestry, China.
    Tang, Bin
    Zhengzhou University, China.
    Jin, Yanghao
    KTH Royal Institute of Technology, Sweden.
    Zaini, Ilman Nuran
    KTH Royal Institute of Technology, Sweden.
    Shi, Ziyi
    KTH Royal Institute of Technology, Sweden.
    Wang, Wujun
    KTH Royal Institute of Technology, Sweden.
    Martin, Andrew
    KTH Royal Institute of Technology, Sweden.
    Younesi, Reza
    Uppsala University, Sweden.
    Sandström, Linda
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Jönsson, Pär G.
    KTH Royal Institute of Technology, Sweden.
    Yang, Weihong
    KTH Royal Institute of Technology, Sweden.
    Han, Tong
    KTH Royal Institute of Technology, Sweden.
    Carbon-negative valorization of biomass waste into affordable green hydrogen and battery anodes2023In: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487Article in journal (Refereed)
    Abstract [en]

    The global Sustainable Development Goals highlight the necessity for affordable and clean energy, designated as SDG7. A sustainable and feasible biorefinery concept is proposed for the carbon-negative utilization of biomass waste for affordable H2 and battery anode material production. Specifically, an innovative tandem biocarbon + NiAlO + biocarbon catalyst strategy is constructed to realize a complete reforming of biomass pyro-vapors into H2+CO (as a mixture). The solid residues from pyrolysis are upgraded into high-quality hard carbon (HCs), demonstrating potential as sodium ion battery (SIBs) anodes. The product, HC-1600-6h, exhibited great electrochemical performance when employed as (SIBs) anodes (full cell: 263 Wh/kg with ICE of 89%). Ultimately, a comprehensive process is designed, simulated, and evaluated. The process yields 75 kg H2, 169 kg HCs, and 891 kg captured CO2 per ton of biomass achieving approx. 100% carbon and hydrogen utilization efficiencies. A life cycle assessment estimates a biomass valorization process with negative-emissions (−0.81 kg CO2/kg-biomass, reliant on Sweden wind electricity). A techno-economic assessment forecasts a notably profitable process capable of co-producing affordable H2 and hard carbon battery anodes. The payback period of the process is projected to fall within two years, assuming reference prices of 13.7 €/kg for HCs and 5 €/kg for H2. The process contributes to a novel business paradigm for sustainable and commercially viable biorefinery process, achieving carbon-negative valorization of biomass waste into affordable energy and materials.

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