The current study demonstrates an efficient strategy for slurry hydroprocessing of solid technical lignins and lignin-derived bio-oils. Semibatch hydroprocessing experiments were performed in a lab-scale 1 L reactor using three technical lignins, and bio-oils (Lignol®)derived by derivatisation from two of these lignins. Four different supported molybdenum or tungsten catalysts, as well as an unsupported molybdenum-based catalyst formed in-situ from a lipophilic molybdenum salt, were tested for the hydroprocessing of lignin bio-oils. All tested supported catalysts exhibited good hydrotreating activity with an overall deoxygenation degree over 80%. The molybdenum-based catalysts yielded fractions with slightly lower oxygen content but higher acidity and a broader boiling-point distribution than the tungsten-based alternatives. The unsupported catalyst showed superior activity with a hydrodeoxygenation degree of 90%. Conversion into bio-oils significantly increased lignin reactivity. Potential chemical differences due to lignin origin appeared secondary to factors, such as sugars or ash content. The process was scaled up to a continuous slurry hydroprocessing process with two different molybdenum-based catalysts, and over 20 kg of lignin-containing feedstock (30 wt% lignin) was processed successfully with each catalyst, achieving up to 87% oxygen removal. Characterisation of the fresh and spent catalyst revealed no indications of significant deactivation when lignin-derived bio-oils were used

Biogas and fatty acids produced from agricultural biomasses for industrial use.

The Swedish Industrial Biogas Commission is calling for 10 TWh of biogas/year (via digestion and gasification; by 2030). Current production is about 2 TWh/year, mainly from waste and sludge. The supply of organic waste is not sufficient to produce the required biogas.Agriculture has significant amounts of residual biomass that can be digested (mainly manure and straw). With this fact taken into account, this project report also assumesthat smaller parts of the arable land can be used for growing nitrogen-fixing grass/clover ley for biogas production, perhaps in combination with the production of protein feed for agriculture and fatty acids for industry in a biorefinery concept.It is possible to use manure, straw and ley with smaller amounts of waste in the western part of Sweden (Västra Götaland, Skåne and Halland) to produce 3.5 to 5 TWh of biogas/year in large biogas plants (approx. 100 GWh/plant and year) for use in industry. Co-production of fatty acids and biogas is also possible, e.g. at least 16 plants are needed to cover identified industrial needs.There are good opportunities for Bio-CCS, partly at the biogas plant, when biogas becomes biomethane, and partly in the industry where biomethane is used. Negative emissions possible, corresponding reduction of climate gases when biomethane replaces natural gas (5 TWh biomethane with CCS can reduce CO₂ emissions by about ¾ for the chemical and refinery industry segment). CO2 can also be used for production of emethane (Bio-CCU), but electricity shortages are a likely bottleneck.The price of natural gas (including tax) compared to biogas with existing subsidies is estimated to be relatively similar. The current subsidy system is directed towards manure digestion, which only produces about 1/5 of the potential biogas from agricultural biomass, which is why subsidies need to be modified to produce the biogas in demand. Fatty acids can also be produced using primarily pasture and waste via a biological process at a similar price level as today's fossil-based production method.A future investment in building biorefineries, which generate renewable commodities can be one solution for the industrial green transition, with agricultural biomasses, but this can also contribute to the green transition of the agriculture. Difficulties with the studied system is that it is large with many actors, significant investment is needed to be realized, and clear incentives are needed to become an actor in the system also includingthe farmers, and there are technical and biological uncertainties in function. A clear question is who is prepared to take the lead in realizing this?

In several countries forest-based biofuels are being developed and to some extent also deployed. Fast pyrolysis bio-oil produced from, for example, sawdust, has now been coprocessed in fluid catalytic cracking refinery units in a number of commercial trials. However, this application is limited to about 10% of the total feed, and coprocessing in conventional fixed bed hydrotreaters is necessary to reach the high potential with this feedstock. Feeding and upgrading of fast pyrolysis bio-oil in a fixed bed reactor configuration is still problematic due to the inherent bio-oil properties. Stabilization of reactive compounds in fast pyrolysis bio-oil and mild hydrotreatment in a separate refining unit prior to refinery integration has therefore been developed the past decade. Another approach, presented here, involves complete dewatering of fast pyrolysis bio-oil by azeotropic distillation using mesityl oxide as the solvent, followed by conversion of the abundant hydroxyl compounds via mixed anhydride esterification methodology using an external source of mixed carboxylic acids of different chain lengths originating from renewable tall oil fatty acids, providing a lipophilic feed component. Dewatering and derivatizing were carried out in reactors up to 50 dm3 with a mass ratio of fast pyrolysis bio-oil to tall oil fatty acid of 10:13. The produced lipophilic oils were miscible with a petroleum light gas oil fraction and exhibited superior stability even after accelerated aging at elevated temperature (80 °C). The derivatized oils were thus mixed with light gas oil, with a proportion of 30 wt % derivatized oil in final blends and hydrotreated continuously in pilot fixed bed reactors for 14 days at 4 operating conditions without plugging or excessive exotherms. The test conditions were varied; the reactor pressure was either 55 or 80 bar, temperature 380 or 400 °C, and liquid hourly space velocity either 1 or 2 h-1 during the hydrotreatment. Successful hydrodeoxygenation and desulfurization were accomplished, whereas an increasing nitrogen concentration could be observed in the liquid products with the particular catalyst and reaction conditions employed. The observed hydrogen consumption (15-20 g/kg feed) was compared with the stoichiometric consumption for direct deoxygenation and with typical consumptions for industrial hydrotreated vegetable oil processing. The measured biogenic carbon content in hydrotreated liquid products (26.7%) agreed extremely well with the calculated biogenic carbon content in the hydrotreating feed (26.6%) that consisted of the blend of derivatized oil and petroleum light gas oil. The overall results are very promising since simple unit operations can be used to produce derivatized fast pyrolysis bio-oils that do not need additional standalone hydrotreating units but can be coprocessed in existing ones

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.

The LignoJet project aimed to achieve an intermediate lignin-oil product miscible with fossil feedstock and with a significantly reduced oxygen content. A technical concept for production has been studied that involves combined catalysed depolymerisation and hydrodeoxygenation, so called hydrogenolytic depolymerisation, of kraft lignin. Kraft lignin was separated through membrane ultrafiltration from softwood and eucalyptus black liquor followed by precipitation through LignoBoost technology. A difference in lignin properties was observed between ultrafiltration of softwood and eucalyptus black liquor through 15 and 150kDa ceramic membranes. Lignin-oils with similar oxygen content were produced regardless of origin and fractionation technique. A lignin-oil with favourable properties as precursor for refinery integration for jet fuel production as produced in small-scale batch experiments using nickel-based catalyst. Stable pumpable oils with melting point of less than 25-50 deg C and with 20-30% lower oxygen content and aromatic content were obtained that would be suitable as jet fuel precursors. The estimated production cost was found to be competitive with that of other liquid biofuels, while additional revenues could potentially be achieved by also producing chemical and materials from suitable fractions of the lignin-oil.