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View PDF Version Cutting-edge research for a greener sustainable future www.rsc.org/greenchem Volume 15 | Number 3 | March 2013 | Pages 537–848 ISSN 1463-9262 CRITICAL REVIEW Tom Welton et al. Deconstruction of lignocellulosic biomass with ionic liquids 1463-9262(2013)15:3;1-O Green Chemistry CRITICAL REVIEW View Article Online View Journal | View Issue Deconstruction of lignocellulosic biomass with Cite this: Green Chem., 2013, 15, 550 ionic liquids Agnieszka Brandt,a John Gräsvik,b Jason P. Halletta and Tom Welton*a This paper reviews the application of ionic liquids to the deconstruction and fractionation of lignocellulo- sic biomass, in a process step that is commonly called pretreatment. It is divided into four parts: the first gives background information on lignocellulosic biomass and ionic liquids; the second focuses on the Received 28th August 2012, solubility of lignocellulosic biomass (and the individual biopolymers within it) in ionic liquids; the third Accepted 18th December 2012 emphasises the deconstruction effects brought about by the use of ionic liquids as a solvent; the fourth DOI: 10.1039/c2gc36364j part deals with practical considerations regarding the design of ionic liquid based deconstruction www.rsc.org/greenchem processes. 1. Introduction interest in renewable technologies to replace fossil sources of carbon. One of these technologies is the conversion of During the twentieth century, we came to rely on fossilised biomass to fuels and chemicals in the so-called ‘Integrated organic matter such as coal, gas and oil for the generation of Biorefinery’.1 energy and the production of chemical products. It is now Currently, biofuels are the most significant biomass derived clear that the carbon dioxide produced during combustion of chemicals and are made from edible components of food fossil resources is causing significant climate change. In crops, such as sucrose, starch and vegetable oils. Vegetable addition, the golden age of cheap and abundant supply, at oils are converted to biodiesel, which can be used on its own least for petroleum, will soon pass. This has led to a growing or blended with other diesels. Sugars are converted to ethanol by microbial fermentation. Ethanol can be blended in any ratio with gasoline, being compatible with the existing fleet of cars at low concentrations (5–15%), while flex fuel cars are aDepartment of Chemistry, Imperial College London, London, SW7 2AZ, UK. E-mail: [email protected] able to use any concentration. The fermentation of carbo- Open Access Article. Published on 19 December 2012. Downloaded 9/30/2021 3:16:27 AM. bDepartment of Chemistry, Umeå University, Umeå, Sweden hydrates to ethanol is a truly ancient technology that has more Agnieszka Brandt graduated John Gräsvik was born in 1977 from LMU Munich with a Bache- and in 2005 he obtained a lors in chemistry and biochemis- Master of Science in Engineering try and a degree in chemistry. with a major in chemistry from During her Masters, she investi- Umeå University. In 2008 he gated the production of n- began his PhD studies at the butanol in bacteria. Her next same university and is expected research interest was the frac- to graduate in the summer of tionation of lignocellulosic 2013. His research is focused on biomass with ionic liquids. In ionic liquids and in particular 2011, she completed her PhD at the pretreatment of biomass Imperial College London in this using ionic liquids. In 2011 he Agnieszka Brandt area under the joint supervision John Gräsvik spent 6 months in Tom Welton’s of Tom Welton, David Leak and research group at Imperial Richard Murphy. Notably, she has investigated the impact of the College London studying the physical properties of acids in ionic ionic liquid anion on the effectiveness of the ionic liquid decon- liquid. struction process. Agi is currently the Business Manager of Imper- ial College spin-out Econic Technologies Ltd. 550 | Green Chem., 2013, 15, 550–583 This journal is © The Royal Society of Chemistry 2013 View Article Online Green Chemistry Critical Review recently been applied to the production of biofuels. It is rela- tively easy to bring sucrose and starch feedstocks into a form that can be fermented by microorganisms. Brazilian sugar cane ethanol can save 80% of greenhouse gas emissions (com- pared to gasoline) with current technology, while other options such as corn ethanol provide more modest savings due to the more energy-intensive cultivation of these crops.2 Concerns have been widely expressed that the production of fuels from edible biomass directly competes with food pro- Fig. 1 Conversion of first generation and second generation feedstocks into ethanol via the fermentation route. Adapted from ref. 7. duction and that CO2 emission savings obtained by replacing gasoline with bioethanol may be diminished by CO2 released as a consequence of land use change.3 material into fuels and chemicals are yet to be commercially Lignocellulosic biomass is the most abundant plant developed.6 The increasing complexity of the biomass, from material on our planet and therefore available in much higher sucrose to starch to lignocellulose, leads to additional process quantities (also due to higher yields per area of land) and at steps (Fig. 1). Sucrose, extracted from sugar cane or sugar beet, lower cost than starch and sucrose based materials.1c,4 It has can be directly utilised for yeast fermentation. The starch from been estimated that the US produces enough lignocellulosic corn or other grains is first hydrolysed (depolymerised) to feedstock today to substitute 30% of their liquid transport glucose using enzymes. In order to access the carbohydrates in fuels with biofuels.4 Utilisation of lignocellulose as a biofuel the biomass for biological conversion, an additional decon- feedstock is likely to provide much higher CO2 emission struction step (also commonly called pretreatment or pre-treat- savings.2,5 ment) is required to bring the sugar polymers into a form Lignocellulose is the material that makes up the cell walls suitable for hydrolysis and subsequent fermentation. of woody plants such as trees, shrubs and grasses. It is a com- This additional processing consists of a number of steps: posite material, with three biopolymers, cellulose, hemicellu- feedstock comminution, the actual feedstock deconstruction, lose and lignin, making up ca. 90% of the dry matter. It conditioning of the treated biomass and the hydrolysate (e.g. contains up to 60–70 wt% sugars/carbohydrates but is not uti- detoxification and neutralisation), hydrolysis/depolymerisation lised for food production. Lignocellulosic biomass for indus- of the polysaccharides. The microbial fermentation of mono- trial use can come from various sources: agricultural and saccharides and product recovery (often by distillation) is forest residues, municipal waste such as organic and paper similar to sucrose based processes. The deconstruction of ligno- waste and crops specifically grown for this purpose (dedicated cellulose is likely to account for an important fraction of the biofuel crops). The use of agricultural residues, e.g. cereal energy requirement for biomass processing.8 In addition, the straws and corn cobs, as biorefinery feedstock makes it possi- utilisation of the non-carbohydrate fraction, lignin,9 is highly ble to produce food and fuels using the same land. desirable for the economic viability of any future biorefinery. A major obstacle to competitive lignocellulose utilisation is Therefore, optimisation of the deconstruction step is desired. ff Open Access Article. Published on 19 December 2012. Downloaded 9/30/2021 3:16:27 AM. that cost-e ective technologies for processing lignocellulosic This article comprehensively reviews the field of lignocellulose Jason Hallett received his PhD in Tom Welton received both his chemical engineering from the BSc and DPhil in chemistry from Georgia Institute of Technology. the University of Sussex. He later He joined Imperial College in moved to the University of Exeter 2006 with a Marshall-Sherfield where he was the Demonstrator Postdoctoral Fellowship in Sus- in Inorganic Chemistry. Upon tainable Chemistry and is now a being awarded a Lloyd’sof Research Lecturer in the Depart- London Tercentenary Fellowship ment of Chemistry. He has he moved again to Imperial authored over 60 articles and College, where he has remained holds 4 patents. He has a multi- ever since and is now Professor disciplinary background (organic of Sustainable Chemistry and Jason P. Hallett chemistry/chemical engineering) Tom Welton head of the Chemistry Depart- and his research lies at the ment. He has worked with ionic science–engineering interface. His current research interests liquids since the mid-1980s, studying their structures, interactions involve the solvation behaviour of ionic liquids and the use of with solutes, effects on reactivity and applications. ionic liquids in biorefining, specifically the production of sustain- able chemical feedstocks and lignocellulosic biofuels. This journal is © The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 550–583 | 551 View Article Online Critical Review Green Chemistry deconstruction with ionic liquids, one of several deconstruc- tion options under development. The review covers the area from early development which has partly already been reviewed elsewhere10 and provides an update on recent advances. 1.1 The chemical composition of wood Lignocellulose is a composite material synthesised by plant cells, consisting mainly of polymeric carbohydrates
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