Fractionation of lignocellulosic biomass with the ionic liquid 1-butylimidazolium hydrogen sulfate

Verdía, Pedro; Brandt, Agnieszka; Hallett, Jason P.; Ray, Michael J.; Welton, Tom

doi:10.1039/c3gc41742e

Cited by 154 publications

(140 citation statements)

References 16 publications

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“…[253] Afurther possibility is to employ protic ionic liquids (ILs) as a( "catalytic") solvent, affording another variant of the Organosolv process denoted the "Ionosolv" process. [255][256][257][258][259][260][261] As cellulose is insoluble in the new protic ILs,t he process contrasts starkly with earlier methods for acid-catalysed depolymerisation of cellulose in dialkylimidazolium ILs. [262][263][264][265][266][267] Accordingly,t he acidic IL solvent acts specifically on lignin and hemicellulose.Delignification of lignocellulosic biomass (Miscanthus giganteus)i sa chieved at 120 8 8Cb yt he cleavage of b-ether units [268] employing, e.g.,1 -butylimidazolium hydrogen sulfate or triethylammonium hydrogen sulfate, as as olvent.…”

Section: Other Fractionation Methods Based On Acid Catalysismentioning

confidence: 99%

“…[262][263][264][265][266][267] Accordingly,t he acidic IL solvent acts specifically on lignin and hemicellulose.Delignification of lignocellulosic biomass (Miscanthus giganteus)i sa chieved at 120 8 8Cb yt he cleavage of b-ether units [268] employing, e.g.,1 -butylimidazolium hydrogen sulfate or triethylammonium hydrogen sulfate, as as olvent. [255][256][257][258][259][260][261] Thel ignin fraction dissolves in these ILs, and can be precipitated by the addition of water. Adopting this procedure,i ti sp ossible to recycle the IL for successive fractionation cycles.E ffective application of ILs towards biomass valorisation has been previously hindered by (amongst other reasons) the high costs of IL precursors and synthesis,t he derivatising nature of the IL, and difficulties regarding the separation and recycling of the IL.…”

Section: Other Fractionation Methods Based On Acid Catalysismentioning

confidence: 99%

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Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

et al. 2016

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Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine‐tuning of multiple “upstream” (i.e., lignin bioengineering, lignin isolation and “early‐stage catalytic conversion of lignin”) and “downstream” (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a “beginning‐to‐end” analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding of lignin's biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.

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Section: Other Fractionation Methods Based On Acid Catalysismentioning

confidence: 99%

Section: Other Fractionation Methods Based On Acid Catalysismentioning

confidence: 99%

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

et al. 2016

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“…An increase in crystallinity index is often indicative of hemicellulose and/or lignin removal and hydrogen sulfate ionic liquids have been shown to be effective delignification agents in other studies. 3,15 Hence we investigated the composition of the recovered solid in more detail.…”

Section: Suitability Of Pulp For Enzymatic Hydrolysismentioning

confidence: 99%

“…The ILs were designed for this study on the basis that (i) ILs based on the hydrogen sulfate anion have proven to be effective delignifiers, (ii) protic cations in [HSO 4 ] -ILs appear to work as well as their non-protic analogues (iii) protic ILs can be produced more cheaply due to cheaper starting materials and ease of synthesis 15 , and (iv) many alkylamines are produced in large quantities at low cost today; ethyl-and ethanolamines are particularly attractive in this regard. The range of ionic liquids was selected so that the effect of number of alkyl chains could be investigated; therefore mono-, di-, and triethylammonium hydrogen sulfate were synthesized.…”

Section: Il Design Rationalementioning

confidence: 99%

Design of low-cost ionic liquids for lignocellulosic biomass pretreatment

et al. 2015

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The cost of ionic liquids (IL) is one of the main impediments to IL utilization in the cellulosic biorefinery, especially in the pretreatment step. In this study, a number of ionic liquids were synthesized with the goal of optimizing solvent cost and stability whilst demonstrating promising processing potential. To achieve this, inexpensive feedstocks such as sulfuric acid and simple amines were combined into a range of protic ionic liquids containing the hydrogen sulfate [HSO 4 ] -anion. The performance of these ionic liquids was compared to a benchmark system containing the IL 1-ethyl-3-methylimidazolium acetate [C 2 C 1 im][OAc]. The highest saccharification yields were observed for the triethylammonium hydrogen sulfate IL, which was 75% as effective as the benchmark system. Techno-economic modeling revealed that this promising and yet to be optimized yield was achieved at a fraction of the processing cost. This study demonstrates that some ILs can compete with the cheapest pretreatment chemicals, such as ammonia, in terms of effectiveness and process cost, removing IL cost as a barrier to the economic viability of IL-based biorefineries.

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“…18,19 Different strategies are followed, from disrupting the lignocellulosic cell wall structure without separation, [20][21][22][23] to selectively isolating lignin, hemicelluloses and cellulose. 15,24,25 While the ultimate goal of pretreatment for enzymatic hydrolysis and fermentation is the isolation of a maximum amount of fermentable sugar, process economics are influenced by a number of factors, such as the number of process steps, the cost and recyclability of additives or solvents, energy requirements, and reactor size, which all influence capital and/or operating costs. 26,27 Reactor size specifically is dictated by the biomass to liquid ratio and residence time.…”

Section: Introductionmentioning

confidence: 99%

Rapid pretreatment of Miscanthus using the low-cost ionic liquid triethylammonium hydrogen sulfate at elevated temperatures

et al. 2018

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Deconstruction with low-cost ionic liquids (ionoSolv) is a promising method to pre-condition lignocellulosic biomass for the production of renewable fuels, materials and chemicals. This study investigated process intensification strategies for ionoSolv pretreatment of Miscanthus × giganteus with the low-cost ionic liquid triethylammonium hydrogen sulfate ([TEA] [HSO 4 ]) in the presence of 20 wt% water, using high temperatures and a high solid to solvent loading of 1 : 5 g/g. The temperatures investigated were 150, 160, 170 and 180°C. We discuss the effect of pretreatment temperature on lignin and hemicellulose removal, cellulose degradation and enzymatic saccharification yields. We report that very good fractionation can be achieved across all investigated temperatures, including an enzymatic saccharification yield exceeding 75% of the theoretical maximum after only 15 min of treatment at 180°C. We further characterised the recovered lignins, which established some tunability of the hydroxyl group content, subunit composition, connectivity and molecular weight distribution in the isolated lignin while maintaining maximum saccharification yield. This drastic reduction of pretreatment time at increased biomass loading without a yield penalty is promising for the development of a commercial ionoSolv pretreatment process.

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Fractionation of lignocellulosic biomass with the ionic liquid 1-butylimidazolium hydrogen sulfate

Cited by 154 publications

References 16 publications

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

Design of low-cost ionic liquids for lignocellulosic biomass pretreatment

Rapid pretreatment of Miscanthus using the low-cost ionic liquid triethylammonium hydrogen sulfate at elevated temperatures

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