WO2021058483A1 - Procédé de production de composants de lignine à partir de biomasse lignocellulosique - Google Patents

Procédé de production de composants de lignine à partir de biomasse lignocellulosique Download PDF

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WO2021058483A1
WO2021058483A1 PCT/EP2020/076433 EP2020076433W WO2021058483A1 WO 2021058483 A1 WO2021058483 A1 WO 2021058483A1 EP 2020076433 W EP2020076433 W EP 2020076433W WO 2021058483 A1 WO2021058483 A1 WO 2021058483A1
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lignin
lignocellulosic biomass
components
biomass
process according
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PCT/EP2020/076433
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English (en)
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Iwona CYBULSKA
Filippo BRIENZA
Damien DEBECKER
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Université Catholique de Louvain
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class

Definitions

  • the present invention relates generally to the field of biorefinery, and more specifically to the field of processing of lignocellulosic biomass into valuable components that can be used in downstream processing.
  • the present invention relates in particular to a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, and to the use of such components in the production of chemicals, such as fuels, polymers, bulk or fine chemicals, pharmaceuticals, antimicrobial agents, etc. or in pulp and paper industry.
  • Biorefinery and biomass will play an increasingly crucial role over the coming decades.
  • Biorefinery is a refinery that converts biomass to energy and other beneficial bioproducts such as chemicals. It involves the sustainable processing of biomass into a spectrum of bio-based products such as food, feed, chemicals, materials, and bioenergy including biofuels, power and/or heat. As refineries, biorefineries can provide multiple chemicals by recovering from an initial raw material, i.e. the biomass, multiple intermediates that can be further converted into value-added products. For instance, the conversion of biomass to different forms of energy, has received growing attention as a mean of replacing energy and other end-products derived from fossil raw materials. In addition, biomass is considered a major renewable source for bulk chemicals and materials.
  • Lignocellulosic biomass primarily consists of three polymeric components: cellulose (C 6 -sugars), hemicellulose (mainly Cs-sugars) and lignin.
  • Cellulose is a polysaccharide of glucose monomers linked by b-1 ,4 glucosidic bonds
  • hemicellulose is a polysaccharide of mixed composition and structure, containing a large proportion of pentose sugars linked by b-1 ,4 bonds.
  • Lignocellulosic plant materials also contain extractives, which represent a minor fraction (typically between 5% and 15%). Extractives contain large numbers of lipophilic and hydrophilic constituents.
  • lignocellulosic biomass The rigid matrix of intertwined cellulose, hemicellulose and lignin polymers present in lignocellulosic biomass complicates the isolation and recovery of valuable components thereof, and the processing thereof towards fuels and chemicals.
  • lignin is a challenging task in part due to lignin’s recalcitrant, irregular and complex polymeric structure, which has severely complicated the development of controlled methods for recovering lignin and derivatives thereof for the production of fine chemicals.
  • Another major obstacle in the valorization of lignin is lignin’s strong tendency towards irreversible re-polymerisation and degradation.
  • Lignin is generally present in lignocellulosic biomass in an amount of about 15 to 30% by weight.
  • lignin is unusual because of its heterogeneity and lack of a defined primary structure.
  • various lignins differ structurally depending on biomass source and subsequent processing, but one common feature is a backbone consisting of various substituted phenylpropane units that are bound to each other via aryl ether or carbon-carbon linkages. They are typically substituted with methoxyl groups and the phenolic and aliphatic hydroxyl groups provide sites for e.g. further functionalization.
  • Depolymerized lignin i.e. lignin degraded into small units or molecules that may be further processed.
  • Depolymerized lignin can for instance be obtained by deployment of pretreatment methods, such as the kraft and organosolv methods.
  • pretreatment methods involve a chemical treatment of the biomass.
  • pretreatment methods have the major disadvantage that they lead to lignin components of which the molecular structure is significantly altered with respect to native lignin, inevitably limiting their valorization.
  • lignins obtained from different sources such as e.g. black liquor, red liquor, Kraft lignin, sulfonated lignin, precipitated lignin, filtrated lignin, acetosolv or organosolv lignin, are depolymerized via hydrothermal treatment in an aqueous solution containing a sulphur-based reducing agent.
  • the disclosed process thus relies on the depolymerisation of chemically pre-treated lignin.
  • the output of such a process is an aqueous solution of lignin, possessing a lower molecular weight compared to the initial material.
  • the depolymerized lignin can then undergo esterification to increase its lipophilicity, followed by mixing with an organic carrier and hydrocracking or catalytic cracking to give a final product.
  • WO 2017/174207 Another example of a process, wherein chemically pre-treated lignin is subjected to depolymerisation thereof is given in WO 2017/174207.
  • This document discloses a process comprising a series of consecutive steps for the production of functionalized lignin derivatives from lignocellulosic biomass.
  • This document discloses the step of subjecting lignocellulosic material to pulping.
  • the pulping method adopted can be any existing pulping method such as e.g. Kraft pulping, sulfite pulping, soda pulping, organosolv pulping, etc.
  • pulp is separated from the liquid process stream(s), lignin-derived components are isolated from the liquid process stream(s) and are depolymerised by subjecting these to thermal decomposition or chemical decomposition, e.g. by means of oxidative cracking with oxidizing agents and homo/heterogeneous catalysts; reductive cracking with H2 and heterogeneous catalysts; enzymatic decomposition; photooxidation; treatment in ionic liquids.
  • thermal decomposition or chemical decomposition e.g. by means of oxidative cracking with oxidizing agents and homo/heterogeneous catalysts; reductive cracking with H2 and heterogeneous catalysts; enzymatic decomposition; photooxidation; treatment in ionic liquids.
  • Another technique involves catalytic organosolv fractionation. This technique allows to simultaneously fractionate lignocellulose into its main components and to treat lignin by disruption of the polymeric network, resulting in the production of phenolic monomers and oligomers.
  • WO 2015/080660 discloses a method for the depolymerization of lignin from biomass, involving the use of precious metal catalysts such as palladium-based catalysts, and a mixture of organic solvent and water. Another example thereof is given in Van den Bosch et al. (2015: Energy & Environmental Science, Vol. 8, pp.
  • One object of the invention is to provide a process for producing lignin components from lignocellulosic biomass without using a catalyst.
  • the present invention further aims to provide a process for producing lignin components from lignocellulosic biomass which is cost effective, easy to carry out, and more environmentally friendly.
  • the invention also aims to provide a process for treating lignocellulosic biomass which is a more economically viable integrated biorefinery concept.
  • the present invention further aims to provide a process wherein the number of operational steps is minimized.
  • the invention also aims to provide a providing concomitant (simultaneous) lignocellulosic biomass fractionation and lignin depolymerization.
  • the processes as disclosed herein are of particular relevance in the field of biorefinery.
  • the present invention in particular relates to a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said process involves a depolymerization or disruption of the polymeric structure of the lignin in the lignocellulosic biomass using a solvent-based approach and in the absence of a catalyst.
  • the lignocellulosic biomass processed in accordance with the present invention is in particular provided as solid biomass.
  • the present invention provides a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin, said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting said lignocellulosic biomass with a composition comprising a reducing agent, preferably a sulphur containing reducing agent, and a solvent and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers.
  • a process is provided wherein the lignocellulosic biomass is not chemically treated prior to contacting with said composition.
  • the invention provides a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin, said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting said lignocellulosic biomass with a composition comprising a reducing agent, wherein said reducing agent is a sulphur containing reducing agent, and a solvent,
  • said solvent is a mixture of an organic solvent and water, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and wherein said lignocellulosic biomass provided in step a) is not chemically treated prior to contacting with said composition. Also preferably, a process is provided wherein the lignocellulosic biomass provided in step a) is mechanically treated prior to contacting with said composition to reduce the size of said biomass.
  • a process wherein, when said solvent is a mixture of an organic solvent and water, said process comprises the step of obtaining saccharide components from said lignocellulosic biomass and isolating and recovering said saccharide components.
  • the invention provides lignin components comprising lignin monomers, lignin dimers and lignin oligomers obtained or obtainable from lignocellulosic biomass by a process as disclosed herein, wherein said lignin components comprise lignin monomers in an amount of at least 3% based on the total weight of the lignin components, and preferably unsaturated lignin monomers in an amount of at least 1%, preferably at least 3%, based on the total weight of the lignin components.
  • the present invention provides saccharide components obtained or obtainable from lignocellulosic biomass by a process as disclosed herein, wherein said components comprise C5 and C6 saccharides at a weight ratio of C6 to C5 carbohydrates comprised between 20:1 to 1.2:1 , and for instance between 15:1 and 1.5:1 , or between 10:1 and 2: 1 .
  • the present invention relates to various uses of lignin components and saccharide components as disclosed herein, for instance in the production of chemicals, such as bulk and fine chemicals, in the production of fuels, as additives, or in pulp and paper industry.
  • Another application includes the use of lignin components, such as lignin oil, in the antimicrobial agents production.
  • the present invention thus provides a process wherein valuable components, and in particular lignin components, are provided directly from the lignocellulosic biomass, i.e. without needing to first isolate the lignin from the biomass.
  • the lignocellulosic biomass is contacted as a solid biomass with the composition comprising the solvent and the reducing agent, and preferably the organic solvent and the sulphur containing reducing agent.
  • the lignocellulosic biomass is not chemically treated prior to contacting it with said composition in step b).
  • the lignocellulosic biomass which is provided as the substrate in a process according to the invention is thus applied as raw material, meaning that the solid biomass has not undergone any chemical treatment or processing prior to being subjected to the process of the invention. It was surprisingly found by the Applicant that the treatment of raw lignocellulosic biomass in an organic solvent, possibly in combination with water, in presence of a sulphur-containing reducing agent, permits to obtain a direct depolymerization of native lignin concomitantly to lignocellulose fractionation. It is unexpected that present process allows to simultaneously obtain lignocellulosic biomass fractionation and lignin depolymerization, especially as the process of the invention is carried out in the absence of a catalyst.
  • the present invention provides processes that advantageously provide for effective biomass delignifi cation and lignin depolymerization, providing high delignifi cation yields of the lignocellulosic biomass, and yielding lignin monomers, dimers and oligomers, while at the same time preserving saccharide components that are contained in the biomass for further isolation recovery and use.
  • the present process advantageously does not involve the use of a catalyst, and avoids all drawbacks related to such use.
  • a process according to the invention allows obtaining components derived from the lignocellulosic biomass with specific compositions, which facilitates their use in specific downstream applications.
  • the processes according to the present invention are cost-effective, and easy to carry out, and may advantageously also be integrated into pulping processes.
  • Figure 1 shows MWD profiles of lignin oil obtained from certain experiments reported in example 5 that were carried out at different weight ratios Na 2 S 2 0 4 :biomass.
  • Figure 2 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 5 that were carried out under different reaction times.
  • Figure 3 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 5 that were carried out at different initial nitrogen pressures.
  • Figure 4 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 5 that were carried out using different solvent compositions.
  • Figure 5 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 5 that were carried out at different temperatures.
  • Figure 6 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 5 that were carried out at different biomass concentrations.
  • Figure 7 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 6 that were carried out on herbaceous or softwood biomass using a process of the invention.
  • Figure 8 shows the MWD profiles of lignin oil obtained from certain experiments reported in example 7 that were carried out using different agents.
  • endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • Process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting said lignocellulosic biomass with a composition comprising a reducing agent, preferably a sulphur containing reducing agent, and a solvent and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers.
  • lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin
  • said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting said lignocellulosic biomass with a composition comprising a reducing agent, wherein said reducing agent is a sulphur containing reducing agent, and a solvent,
  • step a) wherein said solvent is a mixture of an organic solvent and water, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and wherein said lignocellulosic biomass provided in step a) is not chemically treated prior to contacting with said composition.
  • step a) Process according to any one of statements 1 to 6, wherein said lignocellulosic biomass is provided in step a) in the form of particles or powder having a particle size of 10 cm or less, or of 5 cm or less, or of 2 cm or less, or of 1 cm or less or of 5 mm or less, or of 1 mm or less; or of 500 pm or less.
  • the reducing agent is a borohydride, for instance selected from the group comprising sodium borohydride, potassium borohydride, and lithium borohydride.
  • the sulphur containing reducing agent is selected from the group comprising, and preferably consisting of, sodium or potassium dithionite, sodium or potassium sulfite, sodium or potassium thiosulfate, sodium or potassium metabisulfite, sodium or potassium sulfinate, thiourea oxide, thiourea dioxide, thiourea trioxide, sodium or potassium hydroxymethane sulfinate, sodium or potassium hydroxyethane sulfinate, sodium or potassium hydroxypropane sulfinate, sodium or potassium hydroxybutane sulfinate, thiophenol, and sulfur dioxide, or any combination thereof; and preferably is selected from the group comprising, and preferably consisting of, sodium dithionite, potassium dithionite, sodium sulfite, and potassium sulfite, sodium thiosulfate, or any combination thereof, and more preferably is selected from sodium dithionite (NaaSaCU),
  • said solvent is an organic solvent, preferably an alcohol, preferably a C1 to C10 alcohol, and even more preferably a C1 to C5 alcohol.
  • said solvent is an organic solvent
  • said organic solvent is an alcohol, preferably a C1 to C10 alcohol, and even more preferably a C1 to C5 alcohol.
  • said solvent is an organic solvent
  • said organic solvent is an alcohol selected form the group comprising methanol, ethanol, 1-propanol, 2-propanol and butanol, and preferably is methanol or butanol or 2-propanol (isopropanol).
  • said solvent is a mixture of an organic solvent and water, preferably a mixture of an alcohol and water, more preferably mixture of a C1 to C10 alcohol and water, even more preferably a mixture of a C1 to C5 alcohol and water.
  • said solvent is a mixture of an alcohol and water, wherein said alcohol is selected form the group comprising methanol, ethanol, 1-propanol, 2-propanol and butanol, and preferably wherein said alcohol is methanol or butanol or 2-propanol (isopropanol).
  • a reducing agent preferably a sulphur containing reducing agent, more preferably sodium dithionite
  • an organic solvent preferably a solvent as defined herein, preferably butanol.
  • composition as applied in step b) is prepared by providing said reducing agent, preferably a sulphur containing reducing agent in a solid state and dissolving said sulfur reducing agent in said solvent.
  • lignin monomers comprise unsaturated and/or saturated lignin monomers having the formula (I) wherein R 1 and R 3 are independently H or OCH 3 , wherein R 2 is selected from the group consisting of H, OH, CH 3 , CH 2 OH, CHO, COCH 3 , CH 2 CH 3 , (CH 2 ) 2 OH, CH 2 CHO, CH 2 COCH 3 , (CH 2 ) 2 COCH 3 , (CH 2 ) 2 CH 3 , CH 2 CHCH 2 , (CH) 2 CH 3 , (CH 2 ) 3 OH,
  • WLC is the total weight of lignin components
  • WAIL is the total weight of acid insoluble lignin in said lignocellulosic biomass
  • lignin monomer yield (Y M ) of said lignocellulosic biomass is at least 3%, and preferably at least 5%, 6%, 7%, 10%, 12%, 15%; 20%; or 25%, and wherein said lignin monomer yield (Y M ) is expressed as :
  • WLM is the total weight of lignin monomers
  • WAIL is the total weight of acid insoluble lignin in said lignocellulosic biomass
  • WLMS is the total weight of saturated lignin monomers
  • WAIL is the total weight of acid insoluble lignin in said lignocellulosic biomass
  • WLMUS is the total weight of unsaturated lignin monomers
  • WAIL is the total weight of acid insoluble lignin in said lignocellulosic biomass
  • Process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting the lignocellulosic biomass of step a) with a composition comprising a reducing agent, wherein said reducing agent is a sulphur containing reducing agent and a solvent, wherein said solvent is an organic solvent, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and wherein said lignocellulosic biomass provided in step a
  • Process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting the lignocellulosic biomass of step a) with a composition comprising a reducing agent, wherein said reducing agent is a sulphur containing reducing agent and a solvent, wherein said solvent is an organic solvent, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, wherein said lignocellulosic biomass provided in step a)
  • Process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting the lignocellulosic biomass of step a) with a composition comprising a reducing agent, wherein said reducing agent is a sulphur containing reducing agent and a solvent, wherein said solvent is a mixture of an organic solvent and water, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and d) obtaining saccharide components from said
  • Process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass, wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin said process comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting the lignocellulosic biomass of step a) with a composition comprising a reducing agent, wherein said reducing agent is a sulphur containing reducing agent and a solvent, wherein said solvent is a mixture of an organic solvent and water, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and d) obtaining saccharide components from said
  • step a) wherein said lignocellulosic biomass provided in step a) is not chemically treated prior to contacting with said composition, and wherein said composition as applied in step b) is prepared by providing said sulphur containing reducing agent in a solid state and dissolving said sulfur reducing agent in said solvent.
  • Lignin components comprising lignin monomers, lignin dimers and lignin oligomers obtained or obtainable from lignocellulosic biomass by the process of any of statements 1 to 47, wherein said lignin components comprise lignin monomers in an amount of at least 3%, and for instance of at least 5%; 6%, 7%; 10%; 12%; 15%; 20%; 25%, based on the total weight of the lignin components.
  • Lignin components according to statement 48 wherein said lignin components comprise unsaturated lignin monomers in an amount of at least 1%, and for instance of at least 3%; 5%; 7%; 10%; 12%; 15%; 20%; 25%, based on the total weight of the lignin components.
  • Mw weight average molecular weight
  • Saccharide components obtained or obtainable from lignocellulosic biomass by the process of any of statements 1 to 17, 21 to 25, 27 to 41, and 45 to 47, wherein said components comprise C5 and C6 saccharides at a weight ratio of C6 to C5 carbohydrates comprised between 20:1 to 1.2:1, and for instance between 15:1 and 1.5:1, or for instance between 10:1 and 2:1.
  • the present invention thus relates to processes for treating lignocellulosic biomass and for producing lignin components from such lignocellulosic biomass.
  • a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin, said wherein said process comprises the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting said lignocellulosic biomass with a composition comprising a reducing agent, preferably a sulphur containing reducing agent, and a solvent, wherein said solvent is an organic solvent, and obtaining lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers and wherein the lignocellulosic biomass provided in step a)
  • a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin, said wherein said process comprises the steps of: a) providing said lignocellulosic biomass as a solid biomass, b1) preparing a composition comprising a reducing agent, preferably a sulphur containing reducing agent, and a solvent, wherein said solvent is an organic solvent, wherein said composition is prepared by providing said sulphur containing reducing agent in a solid state and dissolving said sulfur reducing agent in said solvent; b2) contacting said lignocellulosic biomass provided in step a) with the composition as prepared in step b1) and isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligo
  • the present invention also provides a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass comprising the steps of: a) providing said lignocellulosic biomass as a solid biomass, b) contacting said lignocellulosic biomass with a composition comprising a reducing agent, preferably a sulphur containing reducing agent, and a solvent, wherein said solvent is mixture of an organic solvent and water, and obtaining
  • lignin components comprising lignin monomers, lignin dimers and lignin oligomers
  • step b) (ii) saccharide components comprising C5 and/or C6 saccharides, c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and d) isolating and recovering said saccharide components comprising C5 and/or C6 saccharides and wherein the lignocellulosic biomass provided in step a) is not chemically treated prior to contacting with said composition in step b).
  • a process for producing lignin components comprising lignin monomers, lignin dimers and lignin oligomers from lignocellulosic biomass wherein said lignocellulosic biomass comprises cellulose, hemicellulose and lignin, said wherein said process comprises the steps of: a) providing said lignocellulosic biomass as a solid biomass, b1) preparing a composition comprising a reducing agent, preferably a sulphur containing reducing agent, and a solvent, wherein said solvent is mixture of an organic solvent and water, wherein said composition is prepared by providing said sulphur containing reducing agent in a solid state and dissolving said sulfur reducing agent in said solvent; b2) contacting said lignocellulosic biomass provided in step a) with the composition as prepared in step b1) and isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lign
  • lignin components comprising lignin monomers, lignin dimers and lignin oligomers
  • step b2 (ii) saccharide components comprising C5 and/or C6 saccharides, c) isolating and recovering said lignin components comprising lignin monomers, lignin dimers and lignin oligomers, and d) isolating and recovering said saccharide components comprising C5 and/or C6 saccharides wherein said process is characterized in that the lignocellulosic biomass provided in step a) is not chemically treated prior to contacting with said composition in step b2).
  • the process of the present invention thus involves a treatment of raw lignocellulosic biomass (e.g. softwood, hardwood or herbaceous materials) in an organic solvent or in a mixture of an organic solvent and water, in presence of a sulphur-containing reducing agent.
  • raw lignocellulosic biomass e.g. softwood, hardwood or herbaceous materials
  • organic solvent e.g. water
  • a sulphur-containing reducing agent e.g. pulp containing retained carbohydrates
  • one organic liquid fraction containing depolymerized lignin components
  • two liquid fractions when a mixture of an organic solvent and water is applied
  • one is an organic liquid fraction (containing depolymerized lignin components) and the other one is an aqueous fraction (containing solubilised carbohydrates).
  • the present process allows to simultaneously fractionate raw biomass and convert native lignin into low molecular weight component within a single reaction step, by directly treating the raw lignocellulosic biomass with a composition that comprises a sulphur- containing reducing agent and an organic solvent, optionally in combination with water.
  • lignocellulosic biomass refers to biomass that comprises or contains cellulose, hemicellulose, and lignin.
  • Lignocellulosic biomass includes, but is not limited to plant parts, fruits, vegetables, wood, chaff, grain, grasses, hay, weeds, roots, bark and any lignocellulose containing biological material or material of biological origin. Plants can be in their natural state or genetically modified, e.g., to increase the cellulosic or hemicellulosic or lignin portion of the cell wall.
  • Lignocellulosic biomass can be derived from agricultural crops, crop residues, trees, wood or woodchips, wood sawdust, grasses, and other sources.
  • Lignocellulosic biomass can also include cell or tissue cultures; for example, lignocellulosic biomass can include plant cell culture(s) or plant tissue culture(s).
  • the lignocellulosic biomass as used herein is non-woody plant material, such as grasses, dicots, monocots, etc.
  • the lignocellulosic biomass as used herein is woody plant material or wood.
  • the woody material or the wood may be any kind of wood, including hardwood and softwood.
  • a non-limiting list of woods includes pine, birch, spruce, maple, ash, mountain ash, redwood, alder, elm, oak, fir, prune, eucalyptus, aspen, hemlock, larch, poplar and beech.
  • the lignocellulosic biomass is hardwood, i.e. wood from angiosperm trees.
  • Preferred examples of hardwood include birch and poplar.
  • the lignocellulosic biomass is softwood, i.e. wood from gymnosperm trees such as conifers.
  • Preferred examples of softwood include spruce or pine.
  • the lignocellulosic biomass as used herein is derived from herbaceous plants and agricultural residues.
  • herbaceous plants and agricultural residues include wheat straw, wheat bran, corn stover, barley straw, sugar cane bagasse, prairie grasses, foxtail grasses, miscanthus, beet pulp, chicory pulp.
  • the lignocellulosic biomass is used in a process according to the invention as solid biomass.
  • the lignocellulosic material is applied as raw material or feedstock.
  • the lignocellulosic material is directly contacted with a composition as defined herein and is not chemically treated prior to contacting with said composition, e.g. it is not chemically treated or modified by oxidation or reduction.
  • raw lignocellulosic biomass is contacted with a composition as defined herein.
  • the lignocellulosic biomass is applied as solid biomass in the present process.
  • solid biomass is used herein as synonym for raw biomass or raw biomass material and refers to biomass that has not been chemically processed or treated.
  • solid biomass (raw biomass) is applied as substrate for the process of the invention, i.e. biomass that has not been subjected to any treatment with any chemical agent prior to being contacted with a composition as defined.
  • Solid biomass may however undergo mechanical pre-treatment prior to being contacted with a composition comprising a reducing agent and a solvent as defined herein, in order to reduce its size or volume.
  • mechanical pre-treatment does not include any use of chemical component(s) or chemical composition.
  • the lignocellulosic biomass provided in step a) is “not chemically treated” prior to contacting with said composition.
  • the term “not chemically treated” as used herein means that the biomass applied in the present processes has not been contacted with or subjected to any reaction with a chemical component or chemical composition.
  • lignocellulosic biomass applied in the present process is mechanically treated prior to contacting with a composition as defined herein to reduce the size of said biomass.
  • the lignocellulosic biomass is provided in step a) in the present process in the form of particles or powder.
  • the biomass may be ground to small size particles or powder using any suitable technique.
  • mechanical size reduction may comprise cutting, chipping, grinding, milling, shredding, shearing, or any combination thereof.
  • the lignocellulosic biomass is provided in step a) of the present invention in the form of particles or powder having a particle size of 10 cm or less, or of 5 cm or less, or of 2 cm or less, or of 1 cm or less, or of 5 mm or less, or of 1 mm or less; or of 500 pm.
  • a lignocellulosic biomass as applied in a process according to the invention is wood, preferably hardwood, and is provided in the form of saw dust or wood chips.
  • a lignocellulosic biomass as applied in a process according to the invention is softwood, and is for example provided in the form of saw dust or wood chips.
  • a lignocellulosic biomass as applied in a process according to the invention is herbaceous biomass.
  • lignocellulosic biomass as defined herein is contacted with a composition comprising, and preferably consisting of, a reducing agent and a solvent.
  • a solvent is an organic solvent as defined herein.
  • said solvent is a mixture of an organic solvent as defined herein and water.
  • a composition as provided herein and as applied in the present process is prepared by providing said reducing agent in a solid state and dissolving said sulfur reducing agent in said solvent, wherein said solvent is an organic solvent or is a mixture of an organic solvent and water.
  • a composition as provided herein and as applied in the present process is prepared by providing said sulphur containing reducing agent in a solid state and dissolving said sulfur reducing agent in said solvent, wherein said solvent is an organic solvent or is a mixture of an organic solvent and water.
  • Reducing agent is an organic solvent or is a mixture of an organic solvent and water.
  • lignocellulosic biomass as defined herein is contacted with a composition comprising a reducing agent.
  • said reducing agent is a reducing agent that does not contain sulphur.
  • said reducing agent may be borohydride, for instance selected from the group comprising sodium borohydride, potassium borohydride, and lithium borohydride.
  • said reducing agent is a sulphur containing reducing agent.
  • a sulphur containing reducing agent as used herein may be selected from the group comprising, and preferably consisting of, dithionite, sulfite, thiosulphate, metabisulfite, sulfinate, thiourea, thiourea oxide, thiourea dioxide, thiourea trioxide, hydroxymethane sulfinate, hydroxyethane sulfinate, hydroxypropane sulfinate, hydroxybutane sulfinate, thiophenol, and sulfur dioxide.
  • the sulphur containing reducing agent is dithionite.
  • the sulphur containing reducing agent is a sulfite or a sulfite forming agent.
  • the sulphur containing reducing agent is a thiosulphate.
  • the sulphur containing reducing agent is a metabisulfite.
  • a non-limiting list of sulphur containing reducing agents that may be used in the present invention include sodium or potassium dithionite, sodium or potassium hydroxymethane sulfinate, sodium or potassium sulfite, sodium or potassium bisulfite, sodium or potassium thiosulfate, or any combination thereof.
  • a sulphur containing reducing agent as used in a process according to the invention is selected from the group comprising, and preferably consisting of, sodium or potassium dithionite, sodium or potassium sulfite, sodium or potassium thiosulfate, sodium or potassium metabisulfite, sodium or potassium sulfinate, thiourea oxide, thiourea dioxide, thiourea trioxide, sodium or potassium hydroxymethane sulfinate, sodium or potassium hydroxyethane sulfinate, sodium or potassium hydroxypropane sulfinate, sodium or potassium hydroxybutane sulfinate, thiophenol, and sulfur dioxide, or any combination thereof.
  • the sulphur containing reducing agent as used in a process according to the invention is selected from the group comprising sodium dithionite (CAS Number: 7775-14-6), potassium dithionite (CAS Number: 14293-73-3), sodium sulfite (CAS Number: 7757-83-7), potassium sulfite (CAS Number: 10117-38-1) sodium thiosulfate (CAS Number: 10102-17-7) and potassium thiosulfate (CAS Number: 10294-66-3).
  • the sulphur containing reducing agent as used in a process according to the invention is sodium dithionite (Na2S2C>4).
  • a process wherein the reducing agent, and preferably the sulphur containing reducing agent, is applied at a concentration of between 1.5 and 40 g/L, and preferably at a concentration of between 3 and 25 g/L.
  • the sulfur containing reducing agent may be applied in a process according to the invention at a concentration of between 1.5 and 40 g/L, and preferably at a concentration of between 3 and 25 g/L.
  • a process wherein the reducing agent, and preferably the sulphur containing reducing agent, is applied in an amount of 5 to 40 wt%, based on the total weight of said lignocellulosic biomass, and preferably in an amount of 6 to 35 wt% or of 7 to 30 wt%, or of 10 to 20 wt%, or of 10 to 17 wt%, based on the total weight of said lignocellulosic biomass.
  • the sulphur containing reducing agent is applied in a process according to the invention in an amount of 5 to 40 wt% based on the total weight of said lignocellulosic biomass, and for instance in an amount of 6 to 35 wt% or of 7 to 30 wt%, or of 10 to 20 wt%, or of 10 to 17 wt%, based on the total weight of said lignocellulosic biomass.
  • a reducing agent as applied in the present process refers to an agent that is in a solid state.
  • a reducing agent as defined herein is used in a solid form (solid state) to prepare a composition as defined herein.
  • a reducing agent as defined is provided in solid form, e.g. the form of a powder, and dissolved in a solvent, preferably an organic solvent, as defined herein to obtain a composition as defined herein.
  • a recducing agent is provided in solid form, e.g. the form of a powder and dissolved in a solvent, preferably in a mixture of an organic solvent and water, as defined herein to obtain a composition as defined herein.
  • a sulphur containing reducing agent as defined herein is used in a solid form (solid state) to prepare a composition as defined herein.
  • a sulphur containing reducing agent is provided in solid form, e.g. the form of a powder, and dissolved in a solvent, preferably an organic solvent, as defined herein to obtain a composition as defined herein.
  • a sulphur containing reducing agent is provided in solid form, e.g. the form of a powder and dissolved in a solvent, preferably in a mixture of an organic solvent and water, as defined herein to obtain a composition as defined herein.
  • the present invention therefore in certain embodiments relates to processes wherein lignocellulosic biomass as defined herein is treated with a composition comprising a solvent, i.e. an organic solvent or a mixture of an organic solvent and water, wherein solid sulphur containing reducing agent is applied in a solid state and contacted with or dissolved in said solvent to form a suitable composition.
  • a solvent i.e. an organic solvent or a mixture of an organic solvent and water
  • solid sulphur containing reducing agent is applied in a solid state and contacted with or dissolved in said solvent to form a suitable composition.
  • the solvent applied in the composition is an organic solvent, preferably an alcohol, more preferably a C1 to C10 alcohol, even more preferably a C1 to C5 alcohol.
  • the organic solvent is an alcohol selected form the group comprising methanol, ethanol, 1-propanol, 2-propanol and butanol, and preferably is methanol or butanol or 2-propanol (isopropanol).
  • the solvent applied in the composition is a mixture of an organic solvent and water, preferably a mixture of an alcohol and water, more preferably a mixture of a C1 to C10 alcohol and water, even more preferably a mixture of a C1 to C5 alcohol and water.
  • the solvent is a mixture of an alcohol and water, wherein said alcohol is selected form the group comprising methanol, ethanol, 1-propanol, 2-propanol (isopropanol) and butanol, and preferably is methanol or butanol or 2-propanol (isopropanol).
  • the volume ratio between the water and the organic solvent is comprised between 10:1 and 1 :10, such as between 7:1 and 1:1 or between 5:1 and 1:1, or between 3:1 and 1 :1 or between 2:1 and 1:1, or between 1 :1 and 10:1, or between 1:1 and 1 :7, or between 1.1 and 1:5, or between 1:1 and 1:3, or between 1 :1 and 1 :2.
  • lignocellulosic biomass is contacted with a composition that comprises, and preferably consists, of an organic solvent and a sulfur containing reducing agent.
  • a composition is applied in a process according to the invention that comprises, and preferably consists of, a mixture of sodium dithionite and methanol.
  • a composition is applied in a process according to the invention that comprises, and preferably consists of, a mixture of sodium dithionite and ethanol.
  • a composition is applied in a process according to the invention that comprises, and preferably consists of, a mixture of sodium dithionite and 1-propanol.
  • a composition is applied in a process according to the invention that comprises, and preferably consists of, a mixture of sodium dithionite and 2-propanol (isopropanol). In an embodiment a composition is applied in a process according to the invention that comprises, and preferably consists of, a mixture of sodium dithionite and butanol.
  • a process according to the invention comprises the step of contacting lignocellulosic biomass with a composition that comprises, and preferably consists, of an organic solvent, a sulfur containing reducing agent and water.
  • a composition comprises a mixture organic solvent and water
  • the volume ratio of organic solvent to water in said composition is preferably comprised between 10:1 and 1:10, such as between 7:1 and 1 :1 or between 5:1 and 1 :1 , or between 3:1 and 1 :1 or between 2:1 and 1 :1 , or between 1:1 and 10:1 , or between 1 :1 and 1 :7, or between 1.1 and 1 :5, or between 1 :1 and 1:3, or between 1 :1 and 1:2.
  • the volume ratio of organic solvent to water in a composition as defined herein is around 1 :1. In another embodiment, the volume ratio of organic solvent to water in a composition as defined herein is around 3:1. In another embodiment, the volume ratio of organic solvent to water in a composition as defined herein is around 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of a sulfur containing reducing agent, preferably selected from the group consisting of sodium dithionite, sodium sulfite and sodium thiosulfate, methanol and water.
  • a composition as herein applied comprises, and preferably consists of, a mixture of a sulfur containing reducing agent, preferably selected from the group consisting of sodium dithionite, sodium sulfite and sodium thiosulfate, and ethanol and water.
  • a composition as herein applied comprises, and preferably consists of, a mixture of a sulfur containing reducing agent, preferably selected from the group consisting of sodium dithionite, sodium sulfite and sodium thiosulfate, and 1-propanol and water.
  • a composition as herein applied comprises, and preferably consists of, a mixture of a sulfur containing reducing agent, preferably selected from the group consisting of sodium dithionite, sodium sulfite and sodium thiosulfate, and 2-propanol and water.
  • a composition as herein applied comprises, and preferably consists of, a mixture of a sulfur containing reducing agent, preferably selected from the group consisting of sodium dithionite, sodium sulfite and sodium thiosulfate, and butanol and water.
  • a sulfur containing reducing agent preferably selected from the group consisting of sodium dithionite, sodium sulfite and sodium thiosulfate, and butanol and water.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium dithionite, methanol and water wherein the volume ratio of methanol to water is between 10:1 and 1 :10, and for instance between 5: 1 and 1 :1 , or between 3: 1 and 1 :1 , or between 1 : 1 and 1 :10, or between 1 : 1 and 1 :5, or between 1 : 1 and 1 :3, and for instance is 3:1 , or 1 :1 , or 1 :3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium dithionite, ethanol and water, wherein the volume ratio of ethanol to water is between 10:1 and 1 :10, and for instance between 5:1 and 1 :1 , or between 3:1 and 1 :1 , or between 1 :1 and 1 :10, or between 1 :1 and 1 :5, or between 1:1 and 1:3, and for instance is 3:1, or 1 :1 , or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium dithionite, 1 -propanol and water, wherein the volume ratio of 1 -propanol to water is between 10:1 and 1:10, and for instance between 5: 1 and 1:1, or between 3: 1 and 1 :1 , or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1, or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium dithionite, isopropanol and water, wherein the volume ratio of isopropanol to water is between 10:1 and 1:10, and for instance between 5:1 and 1:1, or between 3:1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1, or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium dithionite, butanol and water, wherein the volume ratio of butanol to water is between 10:1 and 1:10, and for instance between 5: 1 and 1:1, or between 3: 1 and 1:1, or between 1 : 1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1, or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium thiosulfate (NaaSaCh), methanol and water wherein the volume ratio of methanol to water is between 10:1 and 1:10, and for instance between 5:1 and 1:1, or between 3:1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1 , or 1:1, or 1:3.
  • NaaSaCh sodium thiosulfate
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium thiosulfate, ethanol and water, wherein the volume ratio of ethanol to water is between 10:1 and 1:10, and for instance between 5: 1 and 1:1, or between 3: 1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1, or 1:1, or 1 :3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium thiosulfate, 1-propanol and water, wherein the volume ratio of 1 -propanol to water is between 10:1 and 1:10, and for instance between 5:1 and 1:1, or between 3:1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1 , or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium thiosulfate, isopropanol and water, wherein the volume ratio of isopropanol to water is between 10:1 and 1:10, and for instance between 5: 1 and 1:1, or between 3: 1 and 1:1, or between 1 : 1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1, or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium thiosulfate , butanol and water, wherein the volume ratio of butanol to water is between 10:1 and 1:10, and for instance between 5:1 and 1:1, or between 3:1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1, or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium sulfite (Na2SC>3), methanol and water wherein the volume ratio of methanol to water is between 10:1 and 1:10, and for instance between 5:1 and 1 :1 , or between 3:1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1 :1 and 1 :3, and for instance is 3:1 , or 1 :1 , or 1 :3.
  • Na2SC>3 sodium sulfite
  • methanol and water wherein the volume ratio of methanol to water is between 10:1 and 1:10, and for instance between 5:1 and 1 :1 , or between 3:1 and 1:1, or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1 :1 and 1 :3, and for instance is 3:1 , or 1 :1 , or 1 :3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium sulfite, ethanol and water, wherein the volume ratio of ethanol to water is between 10:1 and 1 :10, and for instance between 5:1 and 1 :1 , or between 3:1 and 1 :1 , or between 1 :1 and 1 :10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1 , or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium sulfite, 1 -propanol and water, wherein the volume ratio of 1 -propanol to water is between 10:1 and 1 :10, and for instance between 5:1 and 1 :1 , or between 3:1 and 1 :1 , or between 1 :1 and 1 :10, or between 1 :1 and 1 :5, or between 1 :1 and 1 :3, and for instance is 3:1 , or 1 :1 , or 1 :3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium sulfite, isopropanol and water, wherein the volume ratio of isopropanol to water is between 10:1 and 1 :10, and for instance between 5:1 and 1 :1 , or between 3:1 and 1 :1 , or between 1 :1 and 1 :10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1 , or 1:1, or 1:3.
  • a composition as herein applied comprises, and preferably consists of, a mixture of sodium sulfite, butanol and water, wherein the volume ratio of butanol to water is between 10:1 and 1:10, and for instance between 5: 1 and 1:1, or between 3: 1 and 1:1 , or between 1:1 and 1:10, or between 1:1 and 1:5, or between 1:1 and 1:3, and for instance is 3:1 , or 1 :1 , or 1 :3.
  • a process according to the invention comprises contacting lignocellulosic biomass with a composition as defined herein at a temperature of 175°C or higher or 190°C or higher or 200°C or higher.
  • One preferred temperature range at which a lignocellulosic biomass as defined herein is contacted with a composition as defined herein is at a temperature comprised between 175°C and 250°C, or between 175°C and 230°C and preferably comprised between 180°C and 23 °C, or between 180°C and 250°C, and for instance comprised between 190°C and 230°C or between 190 °C and 220°C or between 190°C and 210°C, or between 195°C and 210°C, or between 200°C and 225°C.
  • said lignocellulosic biomass as defined herein may be contacted with a composition as defined herein for 0.75 hour or longer; such as for 1 hour or longer, such as for 3 hours or longer, for 6 hours or longer, for 12 hours or longer, and may be performed in an inert atmosphere or in an atmosphere containing inert gas.
  • the biomass and the composition may be stirred or shaken prior to or during the contacting phase.
  • the reaction may be performed at an elevated pressure such as 2 bar or higher, or 4 bar or higher.
  • the elevated pressure may be obtained by performing the reaction in a sealed container.
  • a process according to the invention involves the step of obtaining - besides lignin components as provided herein- saccharide components from the lignocellulosic biomass. While said lignin components are essentially derived from the lignin of said lignocellulosic biomass, said saccharide components are essentially derived from the cellulose and hemicellulose of said lignocellulosic biomass. In accordance with a process as disclosed herein also such saccharide components may be isolated and recovered from the treated biomass.
  • Lignin and saccharide components as defined herein may be isolated and recovered by any suitable technique such as but not limited to filtration, evaporation, distillation or centrifugation or any other suitable technique.
  • a process according to the invention is performed in the absence of a catalyst, such as in the absence of a metal catalyst, in the absence of a transition metal catalyst and/or in the absence of a precious metal catalyst.
  • a process according to the invention comprises the step of contacting lignocellulosic material as provided herein with a composition as provided herein in the absence of a catalyst, such as in the absence of a metal catalyst, in the absence of a transition metal catalyst or in the absence of a precious metal catalyst.
  • a process according to the invention is also performed in the absence of hydrogen gas.
  • a process according to the invention comprises the step of contacting lignocellulosic material as provided herein with composition as defined herein and in the absence of hydrogen gas.
  • a process according to the invention thus advantageously permits to eliminate the use of hydrogen gas and of a precious metal and/or transition metal catalyst.
  • the use of precious/transition metal catalysts and high pressures of hydrogen gas constitute primary limitations to process scale-up.
  • eliminating the use of catalytic systems in accordance with a process according to the invention avoids any problems and costs associated with separation of catalyst from obtained reaction products and catalyst recover/regeneration operations.
  • the possibility to work in absence of hydrogen gas and without initial pressurization of a reactor also offers an advantage in terms of safety of the operation.
  • the present invention provides a process that advantageously enables effective biomass delignifi cation and lignin depolymerization, yielding lignin monomers, dimers and oligomers, in absence of hydrogen gas and of a catalyst, while at the same time preserving saccharide components that are contained in the biomass for further isolation recovery and use.
  • lignin components refers to chemical compounds that are derived from the lignin contained in the lignocellulosic biomass, and comprise, preferably consist of, lignin monomers, lignin dimers and lignin oligomers.
  • lignin components may in certain embodiment be used as synonym for a “lignin composition” that comprises, preferably consists of, lignin monomers, lignin dimers and lignin oligomers.
  • Lignin components are obtained as a result of the chemical modification or depolymerization of lignin present within the initial lignocellulosic biomass when carrying out a process according to the invention.
  • the initial and complex lignin structure present in the biomass is processed into smaller fragments, yielding lignin monomers, lignin dimers (comprising two phenylpropane units), and lignin oligomers (comprising more than two phenylpropane units, with molecular weight not higher than 2000 Da).
  • “Lignin monomers” as used herein include saturated lignin monomers and unsaturated lignin monomers. Saturated lignin monomers as used herein to refer to compounds derived from lignin that have saturated alkyl side chains. Unsaturated lignin monomers as used herein refer to compounds derived from lignin that have unsaturated alkyl side chains.
  • said lignin monomers comprise unsaturated and/or saturated lignin monomers having the formula (I) wherein R 1 and R 3 are independently H or OCH 3 , wherein R 2 is selected from the group consisting of H, OH, CH 3 , CH 2 OH, CHO, COCH 3 , CH 2 CH 3 , (CH 2 ) 2 OH, CH 2 CHO, CH 2 COCH 3 , (CH 2 ) 2 COCH 3 , (CH 2 ) 2 CH 3 , CH 2 CHCH 2 , (CH) 2 CH 3 , (CH 2 ) 3 OH, CH 2 (CH) 2 OH, (CH) 2 CH 2 OH, (CH) 2 CHO, (CH 2 ) 2 CHO and CO(CH 2 ) 2 CH 3 , and wherein R 4 is OH or OCH 3 or OCH 2 CH 3 .
  • Non-limitative examples of saturated lignin monomers that may be obtained with a process according to the invention include but are not limited to 4-propylguaiacol (2-methoxy-4- propylphenol - herein also denoted as “propylguaiacol”), 4-ethylguaiacol (4-ethyl-2- methoxyphenol), vanillin (4-hydroxy-3-methoxybenzaldehyde), syringaldehyde (4-hydroxy- 3,5-dimethoxybenzaldehyde), acetoguaiacone (1-(4-Hydroxy-3-methoxyphenyl)ethanone), acetosyringone (1-(4-hydroxy-3,5-dimethoxyphenyl)ethanone), guaiacylacetone (1-(4- hydroxy-3-methoxyphenyl)propan-2-one), syringylacetone (4-(4-hydroxy-3,5- dimethoxyphenyl)but
  • Non-limitative examples of unsaturated lignin monomers that may be obtained with a process according to the invention include but are not limited to 4-propenylsyringol (2,6- dimethoxy-4-[(Z)-prop-1-enyl]phenol, and herein also denoted as “propenylsyringol”), 4- propenylguaiacol (isoeugenol or 2-methoxy-4-[(£)-prop-1-enyl]phenol, and herein also denoted as “propenylguaiacol”), 4-vinylguaiacol (4-ethenyl-2-methoxyphenol), coniferaldehyde ((£)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enal), coniferyl alcohol (4- [(E)-3-hydroxyprop-1-enyl]-2-methoxyphenol), syringaldehyde (4-hydroxy-3,5- dimethoxybenzaldeh
  • a process as described herein thus allows recovering unsaturated lignin monomers from lignocellulosic biomass. This aspect is unexpected as it implies that the process preserves the double bond functionalities of lignin units, without incurring extensive re-condensation of the depolymerized lignin.
  • a process according to the invention also provides lignin dimers and lignin oligomers.
  • “Lignin dimers” as used herein refer to compounds derived from lignin comprising two linked lignin monomers as defined herein.
  • Non-limitative examples of lignin dimers that may be obtained with a process according to the invention include but are not limited to guaiacylglycerol-p-guaiacyl ether, veratrylglycerol- -guaiacyl ether, syringylglycerol-b- guaiacyl ether, pinoresinol, syringaresinol, and dehydrodiisoeugenol.
  • lignin dimers as encompassed by the present invention include lignin dimers having the formula (II), (III) or (IV),
  • R 9 is H, OCH 3 , or (Chh ⁇ CHs, wherein R 5 is H or OH, wherein R 6 is H or CH 2 OH, and wherein R 7 and R 8 are independently H or OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is H, R 5 is H, R 6 is H, R 7 is OCH 3 and R 8 is H.
  • a lignin dimer has formula (IV) wherein R 9 is H, R 5 is H, R 6 is H, R 7 is OCH 3 and R 8 is OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is H, R 5 is H, R 6 is CH 2 OH, R 7 is OCH 3 and R 8 is H.
  • a lignin dimer has formula (IV) wherein R 9 is OCH 3 , R 5 is H, R 6 is H, R 7 is OCH 3 and R 8 is OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is H, R 5 is H, R 6 is CH 2 OH, R 7 is OCH 3 and R 8 is OCH 3 .ln another example, a lignin dimer has formula (IV) whereinR 9 is OCH 3 , R 5 is H, R 6 is CH 2 OH, R 7 is OCH 3 and R 8 is OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is (CH 2 ) 2 CH 3 , R 5 is OH, R 6 is H, R 7 is H and R 8 is OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is (CH 2 ) 2 CH 3 , R 5 is OH, R 6 is CH 2 OH, R 7 is H and R 8 is OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is (OH 2 ) OH 3 , R 5 is OH, R 6 is H, R 7 is OCH 3 and R 8 is OCH 3 .
  • a lignin dimer has formula (IV) wherein R 9 is (CH 2 ) 2 CH 3 , R 5 is OH, R 6 is CH 2 OH, R 7 is OCH 3 and R 8 is OCH 3 .
  • Ligan oligomers refers to compounds derived from lignin comprising more than two linked lignin monomers as defined.
  • a process according to the present invention provides high conversion efficiency, especially in terms of delignification of the initial lignocellulosic biomass, and/or in terms of isolating and recovering valuable components from processed lignocellulosic biomass.
  • conversion efficiency or “conversion rate” or “yield” are used interchangeably herein and have their ordinary meaning as known to those skilled in the art: i.e. they refer in general to the weight of a product made from the weight of a substrate (herein the lignocellulosic biomass). In general, the term can be expressed as a percentage yield of the product from a starting weight of substrate.
  • a process according to the present invention provides high delignification yields of the lignocellulosic biomass.
  • a process as provided herein allows efficient isolation and recovery of lignin components as defined herein from the biomass.
  • the delignification yield of lignocellulosic biomass is defined as the total weight of the lignin components obtained in a process as provided herein over the total weight of lignin present in lignocellulosic biomass provided in said process.
  • the total weight of lignin present in lignocellulosic biomass corresponds herein to the total weight of acid insoluble lignin (AIL) contained in the biomass provided in the process.
  • AIL acid insoluble lignin
  • acid soluble lignin is negligible especially in wood samples and insoluble lignin (also referred to as Klason lignin) is commonly taken as a reference.
  • YD (in %) WLC/WAIL wherein WLC is the total weight of lignin components obtained by a process according to the invention.
  • WAIL is the total weight of acid insoluble lignin contained in the lignocellulosic biomass processed in a process according to the invention.
  • the present invention relates to a process wherein the delignification yield of the lignocellulosic biomass (YD) as defined herein is at least 48%, at least 50%, at least 60%, and for instance at least 75%; 80%; 85%; 90%; 95%; 98%, 99%, or is 100%.
  • the delignification yield of the lignocellulosic biomass (YD) as defined herein is at least 48%, at least 50%, at least 60%, and for instance at least 75%; 80%; 85%; 90%; 95%; 98%, 99%, or is 100%.
  • a process according to the present invention further provides for the isolation and recovery of lignin monomers from lignocellulosic biomass at a considerable yield.
  • lignin monomers may include unsaturated as well as saturated lignin monomers.
  • Y M The yield of lignin monomer isolation and recovery from lignocellulosic biomass is indicated with Y M herein, and is defined as
  • WLM is the total weight of lignin monomers obtained by a process according to the invention.
  • WAIL is the total weight of acid insoluble lignin contained in the lignocellulosic biomass processed in a process according to the invention.
  • the total weight of lignin monomers obtained in a process according to the invention may be determined via a GC-FID procedure such as disclosed in the example section below.
  • the total weight of acid insoluble lignin contained in the initial biomass is determined as indicated herein.
  • the present invention relates to a process wherein the lignin monomer yield (Y M ), as defined herein, is at least 3%, and preferably at least 5%; 6%; 7%; 10%; 12%; 15%; 20%; or 25%.
  • Lignin monomers as obtained with a process according to the invention may comprise or consist of saturated lignin monomers. Therefore, in certain embodiments, a process is provided wherein lignin components are obtained that comprise saturated lignin monomers at a yield of saturated lignin monomers (YMS) of at least 1%, such as at least 3%; 5%; 6%; 7%; 10%; 12%; 15%; 20%; 25%, and wherein said saturated lignin monomer yield (YMS) is expressed as :
  • WLMS is the total weight of saturated lignin monomers obtained by a process according to the invention.
  • WAIL is the total weight of acid insoluble lignin contained in the lignocellulosic biomass processed in a process according to the invention.
  • Lignin monomers as obtained with a process according to the invention may comprise or consist of unsaturated lignin monomers.
  • a process is thus provided wherein lignin components are obtained that comprise or consists of unsaturated lignin monomers at a yield of unsaturated lignin monomers (YMUS) of at least 1%, and preferably at least 3%; 5%; 6%; 7%; 10%; 12%; 15%; 20%; 25%, and wherein said unsaturated lignin monomer yield (YMUS) is expressed as :
  • WLMUS is the total weight of unsaturated lignin monomers obtained by a process according to the invention.
  • WAIL is the total weight of acid insoluble lignin contained in the lignocellulosic biomass processed in a process according to the invention.
  • Lignin components as obtained according to a process of the present invention have a relatively low weight average molecular weight.
  • lignin components are obtained according to a process of the present invention having a weight average molecular weight (Mw) of not more than 2000 g/mol, such as not more than 1500 g/mol, or not more than 1200 g/mol or not more than 1000 g/mol, or not more than 900 g/mol, or not more than 800 g/mol.
  • lignin components as obtained herein have a weight average molecular weight (Mw) comprised between 400 and 2000 g/mol, and for instance comprised between 400 and 1200 g/mol and for instance comprised between 800 and 1500 g/mol.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the lignin components can be determined using techniques that are well known in the art such as gel permeation chromatography as disclosed in the example section below.
  • saccharide components refers to compounds that are derived from lignocellulosic biomass, and preferably from the cellulose and/or hemicellulose of such biomass. In certain embodiments, the term “saccharide components” is used as synonym for “saccharide composition”.
  • Saccharide components as obtained herein may include mono, di-, oligo- or polysaccharides derived from cellulose and hemicellulose in said lignocellulosic biomass.
  • Non limitative examples of saccharide components that may be obtained from a lignocellulosic biomass using a process according to the invention include but are not limited to xylan (i.e. a C5 polysaccharide) and glucan (i.e. a C6 polysaccharide).
  • a process according to the invention permits to recover saccharide components as well as lignin components from lignocellulosic biomass, and thus maximizes the recovery and valorization of components from the lignocellulosic biomass.
  • a process wherein said saccharide components derived from said lignocellulosic biomass comprise C5 saccharides and C6 saccharides, and wherein the weight ratio of C6 to C5 saccharides obtained in said process is comprised between 20:1 to 1.2:1, or between 20:1 and 1.5:1, or between 15:1 and 1.5:1, or between 10:1 and 2:1.
  • a process according to the invention permits to provide saccharide components that are enriched in C6 saccharides as compared to C5 saccharides.
  • saccharide components obtained from a lignocellulosic biomass using a process according to the invention are present the lignocellulosic biomass that remains after processing thereof (i.e. the pulp), and may be isolated and recovered therefrom.
  • the reducing agent such as the sulphur containing reducing agent, as defined herein, is present in the lignocellulosic biomass that remains after processing thereof (i.e. the pulp).
  • Lignin components and/or saccharide components as obtained from lignocellulosic biomass according to a process according to the invention may be used as materials in various downstream processes, for instance in the preparation of fuels, polymers, bulk or fine chemicals, pharmaceuticals, antimicrobial agents, polymers, as additives, etc.
  • lignin components and/or saccharide components as provided herein may be used in refinery processes or as a material for preparing fuel or fuel additives.
  • lignin components and/or saccharide components as provided herein may be used to prepare polymers, such as foams, plastics, rubbers, or to prepare fine chemicals such as aromatic compounds, or as additives.
  • lignin components as disclosed herein include but are not limited to for instance a use in the production of polymers or plastics, such as but not limited to polyurethanes, polycarbonates, epoxy resins, etc, or an application as polymer additive, additive for inks and varnishes, as cement additive.
  • Lignin components and/or saccharide components as obtained from lignocellulosic biomass according to a process of the invention may also be used in pulp and paper industry.
  • Raw (solid) biomass was finely grounded (2 mm particles for herbaceous materials / 0.5 mm particles for woody material) and subjected to two consecutive extractions, first with pure water, then with pure ethanol, using a Soxhlet extractor. The water and ethanol extracts were collected separately and dried at 60 °C overnight, then at 105 °C for 1 hour. The dried residues were weighed to determine the amount of non-volatile water extractives and non-volatile ethanol extractives. Determination of total weight of lignin components
  • a liquid fraction as obtained was separated from the pulp by centrifugation (8000 rpm, 10 min). The liquid fraction was then filtered using glass fiber filters (pore size 1 pm). When two liquid phases were present (organic and aqueous phase), these were separated using a separating funnel.
  • a sample of the selected liquid phase ( ⁇ 5 ml) was dried under nitrogen flow to remove all solvent. The leftover residue underwent a three-fold extraction with dichloromethane and water (6 ml of dichloromethane + 6 ml of water). The extraction was performed under vortexing for 1 minute. The three dichloromethane fractions were then mixed together, and dried using a rotary evaporator. The amount of lignin contained in the sample corresponds to the weight of the dried dichloromethane extract minus the weight of non volatile ethanol extractives. The total weight of lignin components in the selected liquid phase can be calculated with a simple proportion, knowing the volume of the sample analyzed and the total volume of the liquid phase.
  • Raw (solid) lignocellulosic biomass was finely grounded (2 mm particles for herbaceous materials / 0.5 mm particles for woody material) and subjected to two consecutives extractions, first with pure water, then with pure ethanol, using a Soxhlet extractor. The recovered solid was dried overnight at 60 °C, and then at 105 °C for one hour. The extractives-free material obtained was then subjected to a strong acid hydrolysis to measure the content of Klason lignin (acid insoluble lignin). Dried samples were treated with 72% (w/w) sulfuric acid at 30 °C for 1 hour, and then the solutions were diluted with deionized water to achieve 4% (w/w) of sulfuric acid concentration. Diluted samples were autoclaved at 121 °C for 1 hour. The hydrolyzates were filtered through fritted ceramic funnels, and the Klason lignin content was determined as the weight of the acid insoluble residue.
  • Acid insoluble lignin (Klason lignin) content in the extractives-free material was calculated using the formula below: g (W AIL )
  • AIL acid insoluble lignin [g / 100g DM]
  • WAIL weight of AIL after drying at 105 °C [g]
  • DM dry matter [g]
  • Lignin content in an “as received” sample can be calculated as follows:
  • Extractives may be removed from the biomass prior to further processing and typically include waxes, oils, free sugars.
  • a liquid fraction as obtained after reacting a lignocellulosic biomass with a composition as provided herein was separated from the pulp by centrifugation (8000 rpm, 10 min). The liquid was then filtered using glass fiber filters (pore size 1 pm). When two liquid phases were present (organic and aqueous phase), these were separated using a separating funnel.
  • GC analysis was performed using a Thermo Fisher ScientificT race GC Ultra equipped with a Rxi-5Sil MS column and a flame ionization detector (FID). The following operating conditions were used: injection temperature 280 °C, column temperature program: 40 °C (1 min), 2 °C/min to 150 °C, 5 °C/min to 240 °C, 30 °C/min to 300 °C (15 min), detection temperature of 305 °C. Response factors for the different products are determined by calibration with commercial standards or via ECN-based calculation, i.e. based on the Effective Carbon Number Theory.
  • Identification of the monomers may be performed via GC-MS, using a Thermo Fisher Scientific Trace 1310 equipped with a Rxi-5Sil MS column and an ISQ QD Mass Spectroscopy detector. The following operating conditions are used: injection temperature of 280 °C, column temperature program: 40 °C (1 min), 10 °C/min to 300 °C (5 min), detection temperature of 310 °C.
  • a sample of a liquid phase ( ⁇ 5 ml) obtained after reacting a lignocellulosic biomass with a composition as provided herein is separated from the pulp by centrifugation (8000 rpm, 10 min). The liquid is then filtered using glass fiber filters (pore size 1 pm). When two liquid phases are present (organic and aqueous phase), these are separated using a separating funnel.
  • the liquid phase sample is dried under nitrogen flow to remove solvent.
  • the remaining residue undergoes a three-fold extraction with dichloromethane and water (6 ml of dichloromethane + 6 ml of water).
  • the extraction is performed under vortexing for 1 minute.
  • the three dichloromethane fractions are then mixed together, and dried using a rotary evaporator.
  • the extracted lignin is then dissolved in tetrahydrofuran to a concentration of 5 mg/ml.
  • a sample is taken and subsequently filtered through a 0.2 pm polytetrafluoroethylene (PTFE) filter.
  • PTFE polytetrafluoroethylene
  • TDA 305 + UV 2600 TETRA detector
  • RV refractometer
  • IV intrinsic viscosity
  • RALS + LALS light scattering detector
  • Viscotek column CLM3041 (LC5000L, mixed, medium, Org, particle size 10 pm, with effective molecular range up to 4M Da) with 50 cm guard column; Agilent (PN PL1110-6520 (PLgel 5 pm, 100 A pore size, 300 x 7.5 mm)) with guard column (Agilent PL1117-1800, 50x7.5mm, which is PolarGel-M column with particle size 8pm and resolving range up to 2M Da; Malvern (CLM3000 T1000 (Org GPC/SEC Col; 6, 1,500-50 Da), CLM3001 T2000 (Org GPC/SEC Col 6, 5,000-150 Da), CLM3002 T2500 (Org GPC/SEC Col 6, 20,000-300 Da),CLM3003 T3000 (Org GPC/SEC Col 6, 70,000-500 Da), C
  • the recovery of xylan (RC5) and glucan (RC6) in the pulp derived from lignocellulosic material as provided herein is defined as the amount of saccharide measured in the pulp divided by the amount of the same saccharide that was present in the biomass initially applied in a process.
  • a Hi Plex-H column (Biorad) and refractive index detector (RID) were used to determine the concentrations of glucose, xylose, and arabinose at 65 °C using 0.005M H 2 SO 4 as the mobile phase (eluent) with a flow rate of 0.6 ml/min. Equations below summarize the calculations made for the carbohydrates content.
  • C anhydro concentration of the carbohydrates converted into their polymeric form (glucose in form of glucan, etc.) using an anhydro correction (0.88 for pentoses and 0.90 for hexoses) also corrected for any degradation that may have occurred during the dilute-acid step of the hydrolysis according to methodology well known in the art (e.g. by using a recovery factor calculated from replicates enriched with known concentrations of the carbohydrates analyzed) [g/l]
  • V hydrolysate volume of the hydrolysate [ml]
  • Example 1 illustrates a process according to the invention as applied on hardwood.
  • Birch sawdust (Betula pendula, obtained from Centre Alphonse de Marbaix, Corroy-le-Grand, Belgium) was applied as the lignocellulosic starting material.
  • the birch sawdust was milled and sieved to obtain particles smaller than 2 mm, and 3 g thereof was added into a 300 ml stainless steel batch reactor (Parr Instruments Co.) and mixed with a composition consisting of methanol (120 ml) and sodium dithionite (1 g).
  • the ratio of solvent to biomass was 40 ml:1g; the weight ratio of sodium dithionite to biomass was 1:3.
  • the reactor was sealed, flushed with an inert gas and pressured under an initial gas pressure of 30 bar (3 MPa) at ambient temperature.
  • the mixture in the reactor was stirred and the temperature of the reactor was increased to 250 °C (5 °C per minute), at which the pressure reached about 140 bar (about 14 MPa).
  • the reaction was carried out for 3 hours at 250 °C.
  • the liquid /organic phase was isolated from the pulp by centrifugation (8000 rpm, 10 min). The liquid phase was then filtered using glass fiber filters (pore size 1 pm), and treated as indicated above in order to determine the total weight of lignin components obtained. The total weight of lignin components in the liquid phase was then calculated with a simple proportion, taking into account the volume of the sample analyzed and the total volume of the liquid phase.
  • AIL acid insoluble lignin
  • the yield of delignification was determined as the ratio between the total weight of lignin components in the liquid phase and the total weight of acid insoluble lignin (AIL) that was present in the initial biomass.
  • lignin monomer yield was determined as the ratio between the total weight of lignin monomer in the liquid phase determined via GC-FID and the total weight of acid insoluble lignin (AIL) that was present in the initial biomass.
  • Table 1 summarizes the reaction conditions and reports the delignifi cation yield (Y D ) and the lignin monomer yield (YM) as obtained for the different experiments.
  • the present invention allows to obtain delignification yields similar to those reported in the prior art (see Van den Bosch et al. 2015: Energy & Environmental Science, Vol. 8, pp. 1748-1763, and Van den Bosch et al. 2017: Green Chemistry Vol. 19, pp. 3313-33267) for treating lignocellulosic biomass through catalytic organosolv fractionation. While the lignin monomers yields may be higher for reactions reported in this prior art, it is noted that this prior art has the important disadvantage of needing a catalyst to arrive at the reported yields.
  • Example 2 provides different examples of processes according to the invention carried out under different reaction conditions and as applied to birch ( Betula pendula).
  • Birch sawdust obtained from Centre Alphonse de Marbaix, Corroy-le-Grand, Belgium (2 mm particles) was prepared in a same way as explained in example 1 and contacted with a composition consisting of a lower alcohol and a reducing agent (sodium dithionite). The reaction was carried out in a same manner as explained in example 1 using the reaction conditions as listed in Table 2. In the experiments of example 2, the reactor was flushed and pressurized using nitrogen gas. Table 2 lists the delignifi cation yield (YD) and the lignin monomer yield (YM) obtained for the different experiments, as determined in a same manner as explained above in example 1
  • Example 3 is another example of a process according to the invention as applied on hardwood biomass, wherein the hardwood is contacted with a composition wherein the solvent is a mixture of an organic solvent and water.
  • Birch sawdust (Betula pendula, obtained from Centre Alphonse de Marbaix, Corroy-le- Grand, Belgium) was prepared in a same manner as explained in example 1 added into a 300 ml stainless steel batch reactor (Parr Instruments Co.) and mixed with a composition consisting of a butanohwater mixture (volume ratio of 1 : 1 - in the control experiment CE5 no butanol was added) and sodium dithionite as reducing agent (experiments with concentrations of 0.5 g, 1 g or 1.67 g).
  • CE4 no reducing agent was added.
  • the biomass fed to the reactor comprised 25 g/l.
  • the reactor was sealed, flushed and pressured with nitrogen under an initial gas pressure of 0 bar (see experiment IE17) or 30 bar (3 MPa) (see all other listed experiments) at ambient temperature.
  • the mixture in the reactor was stirred and the temperature of the reactor was increased in order to read about 50 bar (about 5 MPa).
  • Table 3 summarizes the reaction conditions applied in the various experiments. The reactions of the different experiments were carried out in the absence of a catalyst and at the indicated temperatures and for the indicated times. Table 3
  • YPEG stands for yield of propenylguaiacol and YRES stands for yield of propenylsyringol
  • RC5 stands for recovery of xylan
  • RC6 stands for recovery of glucan
  • “nd” stands for “not detected”.
  • Van den Bosch et al. (2015) report for the treatment of lignocellulosic biomass through catalytic organosolv fractionation under similar reaction conditions (i.e. particles smaller than 2 mm of birch sawdust ( Betula pendula) treated with methanol in the presence of a ruthenium catalyst for 3 hours at 250°C, biomass feed of 50 g/L and initial hydrogen gas pressure at RT of 30 bar), a delignification yield (YD) of 93%, a lignin monomer yield Y M of 50%, a yield of propylguaiacol and of propylsyringol of 10 and 32% respectively, a yield of propenylguaiacol and propenylsyringol of 0 and 2% respectively, 56% xylan recovery and 95% glucan recovery.
  • the present process allows to recover unsaturated lignin monomers in higher amounts than reported in this prior art.
  • lignin monomer yield is higher when a catalytic system is adopted, the experiments carried out according to the invention illustrate that high delignification yields and considerable yields of lignin monomer components can be obtained even if the reactions were carried out in the absence of a catalyst.
  • a process according to the invention allows recovering lignin components including unsaturated lignin monomers, such as propenylguaiacol; propenylsyringol as well as carbohydrate components such as xylan (C5 saccharide) and glucan (C6 saccharide).
  • Example 4 provides different examples of processes according to the invention carried out under different reaction conditions and as applied to birch ( Betula pendula).
  • birch Betula pendula
  • Birch sawdust (Betula pendula, collected in Belgium) (2 mm particles) was prepared in a same way as explained in example 1 and contacted with a composition consisting of a lower alcohol and a reducing agent (sodium dithionite). The reaction was carried out in a same manner as explained in example 1 using the reaction conditions as listed in Table 5. In the experiments of example 4, the reactor was flushed and pressurized using nitrogen gas. Table 5 lists the delignifi cation yield (YD) and the lignin monomer yield (YM) obtained for the different experiments, as determined according to the above given test methods. In Table 5, “nd” stands for “not determined”.
  • a liquid fraction as obtained was separated from the pulp by centrifugation (8000 rpm, 10 min).
  • the pulp was subjected to consecutive washings: first with the organic solvent employed during the reaction, then with water, before being dried to constant weight at 60 °C.
  • the organic solvent from the washing was added to the liquid fraction.
  • the water from the washing was added to the liquid fraction only when water was already contained in the initial reaction composition.
  • the liquid fraction was then filtered using glass fiber filters (pore size 1 pm). When two liquid phases were present (organic and aqueous phase), these were separated using a separating funnel.
  • a sample of the selected liquid phase ( ⁇ 5 ml) was dried under nitrogen flow to remove all solvent. The leftover residue underwent a three-fold extraction with dichloromethane and water (6 ml of dichloromethane + 6 ml of water). Each extraction was performed under vortexing for 1 minute. The three dichloromethane fractions were then mixed together, and dried using a rotary evaporator to obtain a viscous red-brown oil. The amount of lignin contained in the sample corresponds to the weight of the dried dichloromethane extract minus the weight of non-volatile ethanol extractives (contained in the sample).
  • the total weight of lignin components in the selected liquid phase can be calculated with a simple proportion, knowing the volume of the sample analyzed and the total volume of the liquid phase.
  • the amount of extractives contained in a sample will be proportional to its the volume. Namely, a sample of 5 ml_ will contain an amount of extractives equal to: (5 ml_ / total volume) * total weight of non-volatile ethanol extractives. This is what is subtracted from the dried dichloromethane extract. This procedure corresponds to the procedure given above for examples 1 to 4.
  • Dried samples were treated with 72% (w/w) sulfuric acid at 30 °C for 1 hour (for herbaceous biomass) or 2 hours (for woody biomass), and then the solutions were diluted with deionized water to achieve 4% (w/w) of sulfuric acid concentration. Diluted samples were autoclaved at 121 °C for 1 hour.
  • the hydrolyzates were filtered through pre-weighed fritted ceramic funnels.
  • the funnels with the acid insoluble residues were dried overnight at 105 °C prior to weighing them. Then, the funnels with the dried residues were calcinated in a furnace at 400 °C and the weight of the residual ashes was determined. Finally, the Klason lignin content was determined as the weight of the dried acid insoluble residue, minus the weight of residual ashes.
  • the above-described determination of the residual ash content is taken into consideration when starting from herbaceous biomass materials.
  • the above-described determination of the residual ash content may or may not be applied when starting from woody materials (hardwood/softwood), since in the case of woody materials effects of ash content on the total weight of acid insoluble lignin are negligible.
  • Acid insoluble lignin (Klason lignin) content in the extractives-free material was calculated using the formula below: g (W AIL )
  • AIL acid insoluble lignin [g / 100g DM]
  • WAIL weight of AIL after drying at 105 °C [g]
  • Lignin content in an “as received” sample can be calculated as follows:
  • Extractives may be removed from the biomass prior to further processing and typically include waxes, oils, free sugars. include waxes, oils, free sugars. Determination of total weight of lignin monomers
  • a liquid fraction as obtained after reacting a lignocellulosic biomass with a composition as provided herein was separated from the pulp by centrifugation (8000 rpm, 10 min).
  • the pulp was subjected to consecutive washings: first with the organic solvent employed during the reaction, then with water, before being dried to constant weight at 60 °C.
  • the organic solvent from the washing was added to the liquid fraction.
  • the water from the washing was added to the liquid fraction only when water was already contained in the initial reaction composition.
  • the liquid was then filtered using glass fiber filters (pore size 1 pm). When two liquid phases were present (organic and aqueous phase), these were separated using a separating funnel.
  • GC analysis was performed using a Thermo Fisher ScientificT race GC Ultra equipped with a Rxi-5Sil MS column and a flame ionization detector (FID). The following operating conditions were used: injection temperature 280 °C, column temperature program: 40 °C (1 min), 2 °C/min to 150 °C, 5 °C/min to 240 °C, 30 °C/min to 300 °C (15 min), detection temperature of 305 °C. Response factors for the different products are determined by calibration with commercial standards or via calculations based on the Effective Carbon Number Theory.
  • Identification of the monomers may be performed via GC-MS, using a Thermo Fisher Scientific Trace 1310 equipped with a Rxi-5Sil MS column and an ISQ QD Mass Spectroscopy detector. The following operating conditions are used: injection temperature of 280 °C, column temperature program: 40 °C (1 min), 10 °C/min to 300 °C (5 min), detection temperature of 310 °C.
  • a liquid fraction as obtained after reacting a lignocellulosic biomass with a composition as provided herein was separated from the pulp by centrifugation (8000 rpm, 10 min).
  • the pulp was subjected to consecutive washings: first with the organic solvent employed during the reaction, then with water, before being dried to constant weight at 60 °C.
  • the organic solvent from the washing was added to the liquid fraction.
  • the water from the washing was added to the liquid fraction only when water was already contained in the initial reaction composition.
  • the liquid was then filtered using glass fiber filters (pore size 1 pm). When two liquid phases were present (organic and aqueous phase), these were separated using a separating funnel.
  • a sample of the selected liquid phase ( ⁇ 5 ml) was dried under nitrogen flow to remove all solvent. The remaining residue underwent a three-fold extraction with dichloromethane and water (6 ml of dichloromethane + 6 ml of water). The extraction was performed under vortexing for 1 minute. The three dichloromethane fractions were then mixed together, and dried using a rotary evaporator. The extracted lignin was then dissolved in tetrahydrofuran to a concentration of 5 mg/ml. A sample was taken and subsequently filtered through a 0.2 pm polytetrafluoroethylene (PTFE) filter.
  • PTFE polytetrafluoroethylene
  • Ni is the absorbance measured for molecules possessing a weight M, (proportional to the number of molecules possessing a weight Mi) [a.u.] (absorbance units).
  • a Hi Plex-H column (Biorad) and refractive index detector (RID) were used to determine the concentrations of glucose, xylose, and arabinose at 65 °C using 0.005M H 2 SO 4 as the mobile phase (eluent) with a flow rate of 0.6 ml/min. Equations below summarize the calculations made for the carbohydrates content.
  • C anhydro concentration of the carbohydrates converted into their polymeric form (glucose in form of glucan, etc.) using an anhydro correction (0.88 for pentoses and 0.90 for hexoses) also corrected for any degradation that may have occurred during the dilute-acid step of the hydrolysis according to methodology well known in the art (e.g. by using a recovery factor calculated from replicates enriched with known concentrations of the carbohydrates analyzed) [g/l]
  • V hydroiysate volume of the hydrolysate [ml]
  • Example 5 provides different examples of processes according to the invention as applied on hardwood biomass, wherein the hardwood is contacted with a composition wherein the solvent is a mixture of an organic solvent and water.
  • the solvent is a mixture of an organic solvent and water.
  • Birch sawdust (Betula pendula, collected in Belgium) was prepared in the same manner as explained in example 1, added into a 300 ml stainless steel batch reactor (Parr Instruments Co.) and mixed with a composition consisting of a butanokwater mixture (volume ratio of 1 : 1 - in the control experiment CE8 no butanol was added) and sodium dithionite as reducing agent (experiments with concentrations of reducing agent in a range between 1.6 g/l and 16.7 g/l - in the control experiment CE7 no reducing agent was added). In all listed experiments the biomass was fed to the reactor at concentrations comprised between 25 g/l and 100 g/l.
  • the reactor was sealed, flushed and pressured with nitrogen under an initial gas pressure of 0 bar (see experiment IE39) or 30 bar (3 MPa) (see all other listed experiments) at ambient temperature.
  • the mixture in the reactor was stirred (750 rpm) and the temperature of the reactor was increased up to the chosen setpoint, between 175 °C and 250 °C - in the control experiment CE6 a temperature of 150 °C was applied .
  • the mixture was left to react for a duration between 0.75 hours and 6 hours - in the control experiment CE9 a duration of 0 hours was applied (i.e. the reaction was halted as soon as the temperature reached the setpoint).
  • Table 6 summarizes the reaction conditions applied in the various experiments. The reactions of the different experiments were carried out in the absence of a catalyst and at the indicated temperatures and for the indicated times.
  • YREG stands for yield of propenylguaiacol and YRES stands for yield of propenylsyringol
  • RC5 stands for recovery of xylan
  • RC6 stands for recovery of glucan
  • “nd” stands for “not determined”.
  • Van den Bosch et al. (2015) report for the treatment of lignocellulosic biomass through catalytic organosolv fractionation under similar reaction conditions (i.e. particles smaller than 2 mm of birch sawdust ( Betula pendula) treated with methanol in the presence of a ruthenium catalyst for 3 hours at 250°C, biomass feed of 50 g/L and initial hydrogen gas pressure at RT of 30 bar), a delignification yield (YD) of 93%, a lignin monomer yield YM of 50%, a yield of propylguaiacol and of propylsyringol of 10 and 32% respectively, a yield of propenylguaiacol (YPEG) and propenylsyringol (YPE S ) of 0 and 2% respectively, 56% xylan recovery (RC5) and 95% glucan recovery (RC6).
  • YD delignification yield
  • YM lignin monomer yield
  • the present process allows to recover unsaturated lignin monomers in higher amounts than reported in this prior art.
  • the present invention allows to recover unsaturated lignin monomers in higher amounts than reported in this prior art, with high selectivity for 4-propenylguaiacol and 4-propenylsyringol.
  • lignin monomer yield is higher when a catalytic system is adopted, the experiments carried out according to the invention illustrate that high delignification yields and considerable yields of lignin monomer components can be obtained even if the reactions were carried out in the absence of a catalyst.
  • a process according to the invention allows recovering lignin components including unsaturated lignin monomers, such as propenylguaiacol; propenylsyringol as well as carbohydrate components such as xylan (C5 saccharide) and glucan (C6 saccharide).
  • a simultaneous isolation/fractionation and depolymerization of lignin can be obtained directly starting from raw lignocellulosic biomass and in absence of heterogeneous catalysts and hydrogen gas.
  • the process involves the combined use of a reducing agent, in particular a sulphur-based reducing agent, and an organic solvent, optionally in a mixture with water.
  • FIG. 1 represents the molecular weight distribution profiles as determined by gel permeation chromatograghy (see test methods above) of the lignin oil obtained for various experiments reported in this example 5.
  • the figures 1 to 6 represent the MWD profile for experiments that were grouped per condition, i.e. each figure shows the MWD profiles obtained when changing one experimental condition. Some curves are repeated in multiple figures to facilitate comparisons.
  • the MWD curves have been represented in the figures one above the other (i.e. not superimposed on one another) to facilitate representation of the results. All represented GPC profiles have been shifted up (away from the baseline of the X-axis) to facilitate their representation.
  • Figure 1 shows MWD profiles of lignin oil obtained from certain experiments that were carried out at different weight ratios NaaSaC : biomass (IE34, IE35, IE36 and CE7).
  • Figure 2 shows the MWD profile of lignin oil obtained from certain experiments that were carried out under different durations (IE35, IE37, IE38, CE9).
  • Figure 3 shows the MWD profile of lignin oil obtained from certain experiments that were carried out at different initial nitrogen pressures (IE36, IE39).
  • Figure 4 shows the MWD profile of lignin oil obtained from certain experiments that were carried out using different solvent compositions (IE35, IE40, IE41 and CE8).
  • Figure 5 shows the MWD profile of lignin oil obtained from certain experiments that were carried out at different temperatures (IE36, IE42, IE43, IE44 and CE6).
  • Figure 6 shows the MWD profile of lignin oil obtained from certain experiments that were carried out at different concentrations of biomass (IE35, IE45 and IE46).
  • the present examples 2, 3, 4 and 5 illustrate that the process according to the invention is able to fractionate solid lignocellulosic biomass (i.e. raw biomass that was not pre treated chemically) and convert (depolymerise) native lignin into low molecular weight phenolics within one reaction step by the combined action in that reaction step of a sulphur-based reducing agent (in these examples sodium dithionite) and an organic solvent (examples 2 and 4) or of a sulphur-based reducing agent (in these examples sodium dithionite) and an organic solvent in mixture with water (examples 3 and 5).
  • Example 6 is another example of a process according to the invention as applied on herbaceous or softwood biomass, wherein the biomass is contacted with a composition wherein the solvent is provided as a mixture of an organic solvent and water.
  • Miscanthus sawdust (Miscanthus giganteus, obtained from Centre Alphonse de Marbaix, Corroy-le-Grand, Belgium), wheat straw sawdust (Triticum aestivum, obtained from Centre Alphonse de Marbaix, Corroy-le-Grand, Belgium) and spruce sawdust (Picea abies, collected in Belgium) were prepared in the same manner as explained in example 1 , added into a 300 ml stainless steel batch reactor (Parr Instruments Co.) and mixed with a composition consisting of a butanol:water mixture (volume ratio of 1 :1) and sodium dithionite as reducing agent (the concentration of reducing agent was 4.2 g/l for all experiments). In all listed experiments the raw biomass was fed to the reactor at a concentration of 25 g/l.
  • the reactor was sealed, flushed and pressured with nitrogen under an initial gas pressure of 30 bar (3 MPa) at ambient temperature.
  • the mixture in the reactor was stirred (750 rpm) and the temperature of the reactor was increased up to 200 °C.
  • the mixture was then left to react for 3 hours.
  • lignin components and saccharide components were isolated and recovered.
  • the yield of delignifi cation (YD), the yield of lignin monomers (YM), and the yield of specific unsaturated lignin monomers (propenylsyringol and propenylguaiacol) for the various experiments were determined using the test methods as explained above and are reported in Table 9.
  • Table 9 further lists the yield obtained for specific carbohydrate components (glucan and xylan) as determined using the test methods as explained above.
  • YPEG stands for yield of propenylguaiacol
  • YRES stands for yield of propenylsyringol
  • RC5 stands for recovery of xylan
  • RC6 stands for recovery of glucan.
  • Table 9 The results reported in Table 9 show that the process according to the invention is not only efficient for the treatment of hardwood biomass (see e.g. Examples 2, 3, 4, 5 herein) but can also be applied effectively for the treatment of herbaceous and softwood biomass, hence confirmed process stability and robustness.
  • Van Den Bosch et al. (2015) reported the catalytic organosolv fractionation of miscanthus ( Miscanthus giganteus) and of a mixture of pine and spruce sawdust (treatment with methanol, in the presence of a heterogeneous ruthenium catalyst for 3 hours at 250°C, with biomass feed of 50 g/L and under an initial hydrogen gas pressure at room temperature of 30 bar), and obtained a delignification yield of 56% for miscanthus and 40% for softwood biomass, a lignin monomer yield of 27% for miscanthus and 21% for softwood biomass, but no unsaturated lignin monomers in the products.
  • the present process when the process of the invention is applied to herbaceous and softwood biomass, the present process also allows to recover unsaturated lignin monomers in higher amounts than reported in this prior art, with high selectivity for 4-propenyl guaiacol and 4-propenyl syringol.
  • Average molecular weight of the extracted lignin fractions was determined following the test method described above. Table 10 reports the number average molecular weight (M n ), the weight average molecular weight (M w ) and the polydispersity index (PDI) determined for the lignin oil obtained from the experiments performed. Table 10
  • Figure 7 shows the profile for the molecular weight distribution obtained from gel permeation chromatography of the lignin oil obtained from certain experiments carried out with different biomasses (IE47, IE48 and IE49).
  • the molecular weight distributions shown in Figure 7 illustrates that considerable depolymerization of the isolated lignin fractions can be obtained by applying a process according to the invention to lignocellulosic biomass from different origins.
  • lignin oil becomes more dominant when treating wheat straw (IE48) and spruce sawdust (IE49) as compared to birch (see e.g IE35) and miscanthus sawdust (IE47). It is considered that these differences in lignin depolymerization for lignocellulosic biomass from different sources may be ascribed to nature of the biomass used, e.g. to differences in the content of cleavable b-aryl ether bonds in the lignin structures of these biomass types.
  • Example 7 is another example of a process according to the invention as applied on hardwood biomass, wherein the biomass is contacted with a composition wherein the solvent is a mixture of an organic solvent and water.
  • Birch sawdust (Betula pendula, collected in Belgium) was prepared in the same manner as explained in example 1, added into a 300 ml stainless steel batch reactor (Parr Instruments Co.) and mixed with a composition consisting of a butanol:water mixture (volume ratio of 1 :1) and a reducing agent.
  • the reducing agents adopted were sodium thiosulfate (NaaSaCh) or sodium sulfite (NaaSCh).
  • NaaSaCh sodium thiosulfate
  • NaaSCh sodium sulfite
  • CE10 sodium sulfate (NaaSCU) was employed instead of a reducing agent.
  • the concentration of reducing agent or sodium sulfate was 4.2 g/l for all experiments. In all listed experiments the raw biomass was fed to the reactor at a concentration of 25 g/l.
  • the reactor was sealed, flushed and pressured with nitrogen under an initial gas pressure of 30 bar (3 MPa) at ambient temperature.
  • the mixture in the reactor was stirred (750 rpm) and the temperature of the reactor was increased up to 200 °C. The mixture was then left to react for 3 hours.
  • lignin components and saccharide components were isolated and recovered.
  • the yield of delignifi cation (YD), the yield of lignin monomers (YM), and the yield of specific unsaturated lignin monomers (propenylsyringol and propenylguaiacol) for the various experiments were determined using the test methods as explained above and are reported in Table 11.
  • Table 11 further lists the yield obtained for specific carbohydrate components (glucan and xylan) as determined using the test methods as explained above.
  • YREG stands for yield of propenylguaiacol
  • YRES stands for yield of propenylsyringol
  • RC5 stands for recovery of xylan
  • RC6 stands for recovery of glucan.
  • Average molecular weight of extracted lignin fractions was determined following the test method described above. Table 12 reports the number average molecular weight (M n ), the weight average molecular weight (M w ) and the polydispersity index (PDI) determined for lignin oil obtained from the performed experiments.
  • M n number average molecular weight
  • M w weight average molecular weight
  • PDI polydispersity index
  • Figure 8 shows the MWD profile as obtained from gel permeation chromatography of lignin oil obtained from experiments carried out for the different experiments (IE50, IE51 and CE10).

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Abstract

La présente invention concerne des procédés de production, d'isolement et de récupération de divers composants utiles à partir de biomasse lignocellulosique solide. Plus particulièrement, l'invention concerne un procédé de production de composants de lignine comprenant des monomères de lignine, des dimères de lignine et des oligomères de lignine, à partir de biomasse lignocellulosique, ladite biomasse lignocellulosique comprenant de la cellulose, de l'hémicellulose et de la lignine, ledit procédé comprenant les étapes consistant à : a) fournir ladite biomasse lignocellulosique en tant que biomasse solide, b) mettre en contact ladite biomasse lignocellulosique avec une composition comprenant un agent réducteur contenant du soufre, et un solvant organique, éventuellement présent dans un mélange avec de l'eau, et obtenir des composants de lignine comprenant des monomères de lignine, des dimères de lignine et des oligomères de lignine, et c) isoler et récupérer lesdits composants de lignine. La biomasse lignocellulosique fournie à l'étape a) n'est pas traitée chimiquement avant la mise en contact avec ladite composition à l'étape b) mais est appliquée en tant que biomasse brute. La présente invention concerne également des composants produits à partir de la biomasse lignocellulosique conformément aux procédés décrits et leurs utilisations dans diverses applications.
PCT/EP2020/076433 2019-09-23 2020-09-22 Procédé de production de composants de lignine à partir de biomasse lignocellulosique WO2021058483A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015080660A1 (fr) 2013-11-27 2015-06-04 Kat2Biz Ab Dépolymérisation de lignine dans une biomasse
EP2931968A1 (fr) * 2012-12-12 2015-10-21 Basf Se Utilisation de dithionite de sodium dans un processus de cuisson de cellulose
WO2015199608A1 (fr) 2014-06-27 2015-12-30 Ren Fuel K2B Ab Dépolymérisation de lignine
WO2017174207A1 (fr) 2016-04-07 2017-10-12 Cmblu Projekt Ag Procédé de production de composés dérivés de lignine aromatique de bas poids moléculaire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2931968A1 (fr) * 2012-12-12 2015-10-21 Basf Se Utilisation de dithionite de sodium dans un processus de cuisson de cellulose
WO2015080660A1 (fr) 2013-11-27 2015-06-04 Kat2Biz Ab Dépolymérisation de lignine dans une biomasse
WO2015199608A1 (fr) 2014-06-27 2015-12-30 Ren Fuel K2B Ab Dépolymérisation de lignine
WO2017174207A1 (fr) 2016-04-07 2017-10-12 Cmblu Projekt Ag Procédé de production de composés dérivés de lignine aromatique de bas poids moléculaire

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
S. VAN DEN BOSCH ET AL: "Reductive lignocellulose fractionation into soluble lignin-derived phenolic monomers and dimers and processable carbohydrate pulps", ENERGY & ENVIRONMENTAL SCIENCE, vol. 8, no. 6, 1 January 2015 (2015-01-01), Cambridge, pages 1748 - 1763, XP055302844, ISSN: 1754-5692, DOI: 10.1039/C5EE00204D *
VAN DEN BOSCH ET AL., ENERGY & ENVIRONMENTAL SCIENCE, vol. 8, 2015, pages 1748 - 1763
VAN DEN BOSCH ET AL., ENERGY & ENVIRONMENTAL SCIENCE, vol. 8, pages 1748 - 1763
VAN DEN BOSCH ET AL., GREEN CHEMISTRY, vol. 19, 2017, pages 3313 - 33267

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