Process concepts are being explored to convert lignocellulosic biomass to bio-oil, which can subsequently be upgrade to liquid transportation fuels, e.g. by co-processing in a conventional oil refinery. The field has recently been reviewed in depth (ChemSusChem 2018). The studies carried out of the University of Twente focussed on the conversion processes that exploit high-boiling solvents and operate and moderate temperatures (300-320°C) and moderate pressures (40-60 bars).
One process concept uses the recycled bio-oil product as a liquefaction medium. Recycled bio-oil appeared indeed to be very effective in liquefying the biomass to high degree. However, it becomes increasingly heavy and viscous upon recycling. Hence, a line of investigation is focusing on reducing or mitigating the formation of heavy product. This was attempted either by avoiding their formation e.g. through optimization of process parameters or the use of acid-base additives or by removing the heavy ends prior to recycle e.g. using a novel L/L extraction with T-swing.
Alternatively, we also explored the possibility to avoid recycling the bio-oil with its heavy ends. Here, we explored the use of cheap hydrocarbon solvents that are present in oil refineries. One approach proposes a once-through by liquefying the lignocellulose in a typical FCC feed and feeding the resulting blend directly to the FCC unit. Another approach exploits the natural L/L demixing of bio-oil and hydrocarbons a room temperature to recover and recycle the hydrocarbon solvent.
Beyond developing process concepts, we also try to better understand the chemistry of lignocellulose liquefaction. To this end, we undertook a detailed analysis of the bio-oil and recognized that it’s largely composed of phenolic components, without the water and sugar-like species found in pyrolysis oil. We also studied the liquefaction of the various constituents of lignocellulose and found the carbohydrates to be responsible for the undesired formation of char. In contrast, the lignin was responsible for the formation of heavy liquid products. Finally, we also investigated the role of the solvent in more depth and concluded that the effectiveness of the solvent is due to chemical affinity (or solvation) of sugar-type components, e.g. as expressed in the distance between cellulose and solvent in the Hansen parameter space.
Finally, we also explore alternative uses for the liquefaction oil. For instance, the heavy fraction is solid at room temperature and melt only at elevated temperature. Hence, we are investigating its potential for use as thermoplastic, being as such or as composite that is reinforced with natural fibers.
Publications:
- J.-P. Lange: Lignocellulose liquefaction to biocrude - a tutorial review, ChemSusChem 2018, (DOI: 10.1002/cssc.201702362).
- M.C. Barnés, J. Oltvoort, S.R.A. Kersten, J.-P. Lange; Wood liquefaction - role of solvent, Ind. Eng. Chem. Res., 2017, 56 (3), 635-644.
- M. Castellví Barnés, M.M. de Visser, J.-P. Lange, G. van Rossum and S.R.A. Kersten:Chemistry of the liquefaction of wood and its model components, 2016, J. Anal. Appl. Pyrol. 2017, 125, 136-143.
- S. Kumar, A. Segins, J.-P. Lange, G. Van Rossum and S.R.A. Kersten:Liquefaction of lignocellulosic in light cycle oil: A process concept study, 2015, ChemSusChem, 4 (6), p.p. 3087-3094. (DOI: 10.1021/acssuschemeng.6b00055
- S. Kumar, J.P. Lange, G. van Rossum and S.R.A. Kersten:Liquefaction of lignocellulose: Do basic and acidic additives help out?, 2015, Chem. Eng. J., 278, p.p. 99-104. (DOI: 10.1016/j.cej.2014.12.026)
- M. Castellví Barnés, J.-P. Lange, G. van Rossum and S.R.A. Kersten:A new approach for bio-oil characterization based on gel permeation chromatography preparative fractionation,2015, J. Anal. Appl. Pyrol., 113, p.p. 444-453. (DOI: 10.1016/j.jaap.2015.03.005)
- S. Kumar, J.-P. Lange, G. Van Rossum and S.R.A. Kersten:Bio-oil fractionation by temperature-swing extraction: Principle and application,2015, Biomass and Bioenergy, 83, p.p. 96-104. (DOI: 10.1016/j.biombioe.2015.09.003)
- S. Kumar, J.-P. Lange, G. Van Rossum and S.R.A. Kersten:Liquefaction of lignocellulose in fractionated light bio-oil: Proof of concept and techno-economic assessment,2015, ACS Sust. Chem. & Eng., 3 (9), p.p. 2271-2280. (DOI: 10.1021/acssuschemeng.5b00547)
- S. Kumar, J.-P. Lange, G. Van Rossum and S.R.A. Kersten:Liquefaction of Lignocellulose in Fluid Catalytic Cracker Feed: A Process Concept Study,2015, ChemSusChem, 8 (23), p.p. 4086-4094. (DOI: 10.1002/cssc.201500457)
- S. Kumar, J.P. Lange, G. van Rossum and S.R.A. Kersten:Liquefaction of Lignocellulose: process parameter study to minimize heavy ends,2014, Ind. Eng. Chem. Res., 53 (29), p.p. 11668-11676. (DOI: 10.1021/ie501579v)
- G. van Rossum, W. Zhao, M. Castellvi Barnes, J.-P. Lange, S.R. A. Kersten:Liquefaction of lignocellulosic biomass: solvent, process parameter, and recycle oil screening,2014, ChemSusChem, 7 (1), p.p. 253-259. (DOI: 10.1002/cssc.201300297)