WO2024017949A1 - Raffinerie de biomasse lignocellulosique - Google Patents

Raffinerie de biomasse lignocellulosique Download PDF

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Publication number
WO2024017949A1
WO2024017949A1 PCT/EP2023/070028 EP2023070028W WO2024017949A1 WO 2024017949 A1 WO2024017949 A1 WO 2024017949A1 EP 2023070028 W EP2023070028 W EP 2023070028W WO 2024017949 A1 WO2024017949 A1 WO 2024017949A1
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stream
liquor
lignocellulosic biomass
solvent
alcohol
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PCT/EP2023/070028
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English (en)
Inventor
Bert Sels
Wouter ARTS
Sander VAN DEN BOSCH
Joost Van Aelst
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Katholieke Universiteit Leuven
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Publication of WO2024017949A1 publication Critical patent/WO2024017949A1/fr

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment

Definitions

  • the present invention concerns a lignocellulosic biomass refinery and, more particularly, concerns a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds, comprising the step of contacting the lignocellulosic biomass with a contacting liquor comprising (z) an alcohol, (zz) an acetate ester, with an identical side chain of the alcohol, (zzz) water and (zv) aromatic and carbohydrate compounds originating from lignocellulosic biomass that has been contacted with contacting liquor in the reactor system, to provide a pulp and a liquor enriched with lignocellulosic biomass-derived compounds and, the steps of recycling the solvent components contained in the liquor after conversion for re-entry to the reactor by which the chemical composition of the contacting liquor can be maintained in an efficient way.
  • Lignocellulosic biomass (in particular, but not restricted to, “wood”) is often seen as a suitable alternative for fossil feedstocks for the production of carbon-based chemicals, fuels and materials.
  • Lignocellulosic biomass is a composite material mainly consisting of three quantifiable biopolymers: cellulose, hemicellulose, and lignin.
  • the cellulose portion is a carbohydrate polymer composed of linear chains of glucose units.
  • the hemicellulose represents a family of branched carbohydrate polymers containing both pentoses and hexoses including xylose, arabinose, galactose, glucose and mannose.
  • the hemicellulose also contains acetyl groups which are chemically bound to the hemicellulose pentoses and hexoses.
  • the amount of acetyl groups varies depending on the type of the lignocellulosic biomass (the amount of acetyl groups is referred to as “the acetyl content” and can be expressed on a weight basis) and is typically ranged between 0.1 wt% - 5 wt% of the lignocellulosic biomass (oven-dry basis).
  • Lignin comprises an irregular polymer of aromatic and oxygenated units.
  • a common way to utilise lignocellulosic biomass is to fractionate it in its major constituents.
  • a particular method for the fractionation of lignocellulosic biomass, performed by the pulp and paper industry, utilizes an aqueous mixture of NaOH and Na2S at 130-180 °C.
  • the major portion of the lignin and hemicellulose is readily dissolved in this process, and subsequently undergoes degradation reactions.
  • the lignin and hemicellulose degradation products have low value to the industry, and are primarily incinerated for energy recuperation.
  • the main valuable product of this process is a cellulose-enriched solid (the so called “pulp”), which is used for production of paper and cardboard.
  • Another way to fractionate lignocellulosic biomass, without using sulfur-containing chemicals, is to treat the lignocellulosic biomass with organic solvent(s).
  • organic solvent(s) Often, an alcohol (or mixture of alcohols) is used in combination with mineral acids and/or water in a so-called alcohol-based organosolv pulping process. Due to the good solubility of the lignin in the alcohol, lignin is effectively extracted, with the co-extraction of (some) carbohydrates, mainly originating from hemicellulose, depending on the severity of the process.
  • a major conceptual advantage of using alcohols is that the intact solubilized aromatic, carbohydrate and other compounds (viz., lignin, hemicellulose, extractives, etc.) can be easily recovered from the liquor after fractionation, by distilling off the alcohol or alcohol/water solvents.
  • the carbohydrates can then be removed from the lignin by extraction or with water, thereby precipitating the lignin.
  • lignocellulosic biomass With alcohol-based organosolv pulping, lignocellulosic biomass is effectively converted in its three major constituents: a solid pulp rich in cellulose, a lignin precipitate and an aqueous stream with solubilized carbohydrate compounds, mainly originating from hemicellulose.
  • a disadvantage using alcohol-based organosolv pulping is the high liquor-to-biomass ratio (4: 1 - 10: 1) that is often used in these processes compared to sulfur-based processes ( ⁇ 3: 1). These high liquor-to- biomass ratios are necessary to effectively dissolve the lignin from the lignocellulosic biomass.
  • reaction times are high ( ⁇ 1.5 h to 3 h) with organosolv pulping, large reactors with thick vessel walls are required to process the volumetric liquid flows, often supplied at high pressure and temperature, leading to large capital costs for a high-pressure reactor system.
  • Another disadvantage using the alcohol- based organosolv process is that solvent-like molecules with boiling points similar to the boiling points of the alcohol (and water) solvent are formed during pulping.
  • acetyl moieties of the wood react with the alcohol (and water) to form an equivalent acetate ester (and acetic acid).
  • water contained in the lignocellulosic biomass prior to pulping is released into the liquor during fractiontion thereby increasing the solvent volumes and altering the relative presence of the solvent components, present in the liquor.
  • the recovery of solvents from the liquor is cumbersome, energy-intensive, expensive and has a large CO2 footprint.
  • Bartling et al. discloses a process for pulping lignocellulosic biomass with a methanol/water solvent mixture at volumetric ratio of 9: 1 in the presence of a redox catalyst viz., Ni/C or Pd/C and a hydrogen source viz., hydrogen gas.
  • a redox catalyst viz., Ni/C or Pd/C
  • a hydrogen source viz., hydrogen gas.
  • the pulping of lignocellulosic biomass occurs at high pressure (60 bar) and temperature (200 °C), with a reactor residence time of 3 h and, a high liquor-to-biomass ratio of 9: 1 L/kg (on an oven-dry basis) in a high-pressure reactor system.
  • the pulping step is, after removal of the solid pulp, followed by a two-step distillation process to recover the solvents from the liquor and readjust the solvent composition to the desired volumetric methanol/water ratio before reentry in the reactor system.
  • Techno-economic (TEA) and life-cycle assessment (LCA) of these pulping processes show that this alcohol-based organosolv pulping process incurs large equipment costs for high pressure reactors, high fuel costs for solvent recovery in the distillation steps and has a large CO2 footprint.
  • WO 2022/090364 based on the work of Liao et al. (Liao, et al., Science, 2020, 1385-1390), discloses a similar process for pulping lignocellulosic biomass with methanol in the presence of a Ru/C redox catalyst and hydrogen gas.
  • the pulping of lignocellulosic biomass occurs at high pressure (100 bar) and temperature (250 °C), with a reactor residence time of 1.5 h and, at a high liquor-to-biomass ratio of 4.4: 1 L/kg (on an oven-dry basis) in a high-pressure reactor system.
  • This pulping step is, after removal of the solid pulp, followed by a distillation step to recover the methanol from the liquor.
  • the recovered methanol is then re-entered in the reactor system, but methyl acetate, formed during pulping with methanol, leaves the solvent recycle streams with the hydrogen and off-gases (along with some methanol), which are incinerated for energy recuperation in a trigeneration unit.
  • Methyl acetate is not purified and/or enriched in the methanol solvent recycle. Consequently, acetyl groups, originally present in the lignocellulosic biomass are lost as CO2.
  • the invention is broadly drawn to a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds comprising following steps: a) contacting a lignocellulosic biomass in a reactor system with a contacting liquor comprising (/) an alcohol, (ii) an acetate ester, with a side chain identical to the side chain of the alcohol, (iii) water and (iv) aromatic and carbohydrate compounds originating from lignocellulosic biomass conversion, to provide a pulp and a liquor enriched with lignocellulosic biomass-derived compounds; b) at least partially removing the pulp and the enriched liquor from the reactor system; c) separating pulp, contained in the enriched liquor obtained in step b) from said enriched liquor to generate a purified liquor stream; d) re-entering a part of the purified liquor stream into the reactor system; e
  • An embodiment of the invention concerns a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds comprising following steps: a) comprising contacting a lignocellulosic biomass in a reactor system with a contacting liquor comprising (7) an alcohol, (ii) an acetate ester, with a side chain identical to the side chain of the alcohol, (iii) water and (iv) aromatic and carbohydrate compounds originating from lignocellulosic biomass that has been contacted with contacting liquor in the reactor system, to provide a pulp and a liquor enriched with lignocellulosic biomass-derived compounds; b) at least partially removing the pulp and the enriched liquor from the reactor system; c) separating pulp, contained in the enriched liquor obtained in step b) from said enriched liquor to generate a purified liquor stream; d) re-entering a part of the purified liquor stream into the reactor system; e) separating a part
  • Another embodiment of the invention concerns a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds comprising following steps: a) comprising contacting a lignocellulosic biomass in a reactor system with a contacting liquor comprising (z) an alcohol, (zz) an acetate ester, with a side chain identical to the side chain of the alcohol, (zzz) water and (zv) aromatic and carbohydrate compounds originating from to in the reactor system recycled liquor, to provide a pulp and a liquor enriched with lignocellulosic biomass-derived compounds b) at least partially removing the pulp and the enriched liquor from the reactor system; c) separating pulp, contained in the enriched liquor obtained in step b) from said enriched liquor to generate a purified liquor stream; d) re-entering a part of the purified liquor stream into the reactor system; e) separating a part of the purified liquor stream into a stream comprising the alcohol and the
  • a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds comprising following steps: a. contacting a lignocellulosic biomass in a reactor system with a contacting liquor comprising (z) 0.01 % to 99 % v/v of an alcohol, (zz) 0.01 % to 95 % v/v of an acetate ester, with a side chain identical to the side chain of the alcohol, (zzz) 0.01 % to 95 % v/v of water and (zv) 0.01 % - 95 % v/v of aromatic and carbohydrate compounds originating from the purified liquor stream re-entered in the reactor system as described in step d) and with the volume of the contacting liquor at room temperature and pressure, per mass unit of lignocellulosic biomass on an oven-dry basis being > 1 liter per kg to ⁇ 20 liter per kg and at a temperature of > 100 °C to ⁇ 400 °C
  • a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds comprising following steps: a. contacting a lignocellulosic biomass in a reactor system with a contacting liquor comprising (z) 0.01 % to 99% v/v of an alcohol, (zz) 0.01 % to 95 % v/v of an acetate ester, with a side chain identical to the side chain of the alcohol, (zzz) 0.01 % to 95 % v/v of water and (zv) 0.01 % - 95 % v/v of aromatic and carbohydrate compounds originating from the purified liquor stream re-entered in the reactor system as described in step d) and with the volume of the contacting liquor at room temperature and pressure, per mass unit of lignocellulosic biomass on an oven-dry basis being > 1 liter per kg to ⁇ 12 liter per kg and at a temperature of > 120 °C to ⁇ 300 °C and
  • step c) is performed by centrifugation, filtration or sedimentation or any combination thereof
  • step e) is performed by evaporation, distillation or membrane separation or any combination thereof.
  • step a) the liquor enriched with lignocellulosic biomass-derived compounds is contacted with a catalytic medium comprising a redox catalyst and a hydrogen source in the reactor system.
  • step a) the liquor enriched with lignocellulosic biomass-derived compounds is not contacted with a catalytic medium comprising a redox catalyst and a hydrogen source in the reactor system.
  • carbohydrate pulp also referred to as “pulp” or “solid pulp” means a solid residue, enriched with carbohydrates by removal of lignin, that originates from a lignocellulosic biomass by subjecting the lignocellulosic biomass to a fractionation step.
  • a stream containing aromatic and carbohydrate compounds means a mixture comprising (z) aromatic compounds that have been extracted from the lignin fraction of the lignocellulosic biomass by subjecting the lignocellulosic biomass to a fractionation step, and (zz) carbohydrate compounds that have been extracted from the carbohydrate fraction (hemicellulose and/or cellulose fraction) of the lignocellulosic biomass by subjecting the lignocellulosic biomass to a fractionation step.
  • contacting liquor means a mixture of solvent(s) and/or other chemical compounds, also referred to as “solvent mixture”, by which lignocellulosic biomass is contacted with in a fractionation step.
  • enriched liquor means a liquor in which at least a part of the lignocellulosic biomass-derived products are solubilized, i.e., a liquor which has been enriched therewith, and, which also can contain insoluble lignocellulose-derived products such as pulp, by subjecting the lignocellulosic biomass to a fractionation step.
  • purified liquor means a liquor that has been subject to a solid separation step that, at least partially, removes solids from the liquor to yield a purified liquor.
  • the present invention provides a process for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds.
  • lignocellulosic biomass 11 is provided to a reactor system 10, whereby the lignocellulosic biomass is contacted by a contacting liquor, comprising (z) an alcohol, (zz) an acetate ester, with an identical side chain as the alcohol, (zzz) water and (zv) aromatic and carbohydrate compounds, that is provided to the reactor system by means of a stream 12 containing the alcohol, a recycle stream 20 comprising the alcohol, the acetate ester, water and the aromatic and carbohydrate compounds, and a recycle stream 25 comprising the alcohol and the acetate ester.
  • the lignocellulosic biomass By subjecting the lignocellulosic biomass and the lignocellulosic biomass contacting solvent mixture (i.e., the contacting liquor) in the reactor system 10 at high temperature (> 100 °C) for a treatment time of (> 0.25 h), the lignocellulosic biomass is fractionated into (z) a solid pulp, lean in lignin and enriched with carbohydrates, (zz) solubilized aromatic compounds, originating from the lignin fraction of the lignocellulose, and (zzz) solubilized carbohydrate compounds, originating from the carbohydrate fraction of the lignocellulose.
  • solvent mixture i.e., the contacting liquor
  • a stream 17 rich in pulp is removed directly from the reactor system if the reactor system contains a solid-liquid separation system.
  • the purified liquor stream is fed to a separating system 18 whereby the purified liquor stream is split thereby generating a stream 20 that is re-entered into the reactor system 10 and one other stream 19 with an equal composition as stream 20.
  • the stream 19 is fed to a separating system 21 thereby generating a stream 22 comprising the alcohol and the acetate ester and a stream 23 comprising the aromatic and carbohydrate compounds.
  • the stream 22 is then fed to another separating system 24 whereby the stream 22 is split thereby generating a stream 25 that is reentered into the reactor system 14 and a stream 26 with an equal composition as stream 25.
  • a suitable lignocellulosic biomass for present invention is lignocellulose containing biomass such as wood or pre-processed lignocellulose.
  • This lignocellulosic biomass may be hardwood, softwood and herbaceous biomass, including grasses and straws.
  • Lignocellulosic biomass can be supplied in the form of forestry residues and products (e.g. trees), crops (e.g., energy crops such as grasses and short rotation coppice wood), agricultural residues (e.g. flax shives, sugar cane bagasse), yard waste, municipal solid waste (e.g. newspaper, cardboard, post-consumer wood), industrial waste and products (e.g. sawdust, pellets, chips).
  • the lignocellulosic biomass may comprise fresh feedstock, partially-dried lignocellulosic feedstock, fully dried lignocellulosic feedstock or any combination thereof.
  • the alcohol and the acetate ester, with an identical side chain as the side chain of the alcohol, of the solvent mixture can be any alcohol - acetate ester pair that can be separated from the aromatic and carbohydrate compounds obtained from the lignocellulosic biomass.
  • Suitable side chains include, but are not limited to, methyl, ethyl, w-propyl. isopropyl, w-butyl. isobutyl, w-pcntyl.
  • the solvent mixture comprises 0.01 % to 99 % alcohol v/v, 0.01 % to 95 % acetate esterv/v, 0.01 %to 95 % water v/v and 0.01 % - 95 % v/v of the aromatic and carbohydrate compounds.
  • the present invention provides that water and the acetate ester originate from the lignocellulosic biomass by recycling the solvent mixture that is enriched with water and acetate ester by having contacted the lignocellulosic biomass with the solvent mixture.
  • the lignocellulosic biomass can be contacted with the solvent mixture in the reactor system for a treatment time of 0.25 h to 6 h.
  • the reaction temperature of the solvent mixture in the reactor system can be between 100 °C to 400 °C.
  • the volume of the solvent mixture at room temperature (at RT) and pressure, per mass unit of lignocellulosic biomass on an oven-dry basis can be between 1 liter per kg to 20 liter per kg.
  • a catalytic medium comprising a redox catalyst and a hydrogen source
  • a redox catalyst and a hydrogen source can be present in the reactor system to impact and control the characteristics of the pulp and the aromatic and carbohydrate compounds by contacting the enriched liquor.
  • the redox catalyst and the hydrogen source can assist in depolymerizing lignin fragments that are released when contacting the lignocellulosic biomass with the solvent mixture at high temperature (> 120 °C), by assisting the cleavage of more reactive ether bonds of the lignin polymer through hydrogenolysis.
  • the redox catalyst and the hydrogen source can stabilize reactive aromatic species by chemical reduction impeding the recondensation of reactive lignin fragments that would otherwise be prone to reprecipitate on the pulp or form high-MW lignin precipitates.
  • Reaction products that are formed from the lignocellulosic biomass and solubilized in the solvent mixture by subjecting the lignocellulosic biomass and the solvent mixture contacting the lignocellulosic biomass to a high temperature (> 120 °C) can be supplied to the catalytic medium that has been subjected to a high temperature (> 120 °C).
  • the redox catalyst can be based on a metal for example, but not limited to, Ru, Pd, Pt, Rh, Ni, Ir, Cu, Co, Fe, Os, and the like, or any combination thereof, and a support for example, but not limited to, C, SiO2, ZrO2, SiO2-A12O3, AI2O3, or any combination thereof.
  • the catalyst can be for example, but not limited to, Ru/C, Pd/C, Pt/C, Ni/C, Ni/SiO2, Ni/AhOs, or any combination thereof.
  • the redox catalyst is preferably supplied in the form of pellets.
  • the hydrogen source of the catalytic medium can be hydrogen gas or any other hydrogen source, for example, but not limited to, the alcohol compound(s) of the solvent mixture, the carbohydrate fraction of the lignocellulosic biomass, the lignin fraction of the lignocellulosic biomass, or any combination thereof.
  • such catalytic medium is pressurized under an atmosphere comprising hydrogen gas as hydrogen source.
  • the partial pressure of hydrogen gas (herein referred to simply as “hydrogen pressure”) preferably exceeds atmospheric pressure. More preferably, the hydrogen pressure is in the range of 2-50 bar (at room temperature), such as 5-40 bar, 10-30 bar, or 15-25 bar.
  • a reactor system (10) can be a batch reactor system which comprises of a vessel in which the lignocellulosic biomass and the solvent mixture are loaded before the treatment and the pulp and the enriched liquor are, at least partially, removed after the treatment.
  • such catalytic medium comprising a redox catalyst and a hydrogen source can be present in the batch reactor system.
  • the redox catalyst of the catalytic medium can be present in the same batch reactor vessel comprising the lignocellulosic biomass and the solvent mixture and is preferably physically separated from the lignocellulosic biomass.
  • the redox catalyst can also be present in a vessel or tube external to the first reactor vessel in between which the solvent mixture is continuously pumped, thereby circulating between the vessels during the treatment.
  • the present invention provides that an atmosphere comprising hydrogen gas can be loaded before the treatment to the batch reactor system and/or added and/or removed from the batch reactor system during the treatment.
  • the redox catalyst can be added to the batch reactor system before and/or during the treatment.
  • Multiple batch reactor systems can operate simultaneously.
  • the batch reactor systems can operate in series, whereby the liquor from one system is fed to a next batch reactor system comprising fresh lignocellulosic biomass.
  • the batch reactor systems can also operate in parallel, whereby one or multiple vessels are treating the lignocellulosic biomass whilst one or multiple other vessels are being loaded with lignocellulosic biomass and/or solvent mixture and/or are being unloaded with pulp and enriched liquor.
  • the present invention provides that the reactor system (10) is a flow-through reactor system, which comprises a vessel or tube in which solvent mixture is continuously added and enriched liquor is continuously removed. During the treatment the lignocellulosic biomass remains in the reactor vessel or tube, whereas the aromatic and carbohydrate compounds are removed from the reactor as they are solubilised in the solvent mixture.
  • the catalyst is present within the same tube or vessel. In another embodiment, the catalyst is present in a second vessel or tube (referred to as “second stage”). In this embodiment, the solvent containing solubilized aromatic and carbohydrate compounds is added to the second stage when exiting the vessel or tube containing the lignocellulosic biomass. Hydrogen gas or another hydrogen source needs to be added only to the second stage.
  • the flow-through reactor systems can operate simultaneously.
  • the flow-through reactor systems can operate in series, whereby the liquor from one flow-through reactor system is fed to a next flow-through reactor system comprising lignocellulosic biomass.
  • the flow-through reactor systems can also operate in parallel, whereby solvent mixture is continuously fed to the flow-through reactor systems and enriched liquor is continuously removed from the flow-through reactor systems.
  • the reactor system (10) is a continuous reactor system, which is a vessel or tube wherein the solvent mixture and the lignocellulosic biomass are continuously added and removed as a slurry comprising the pulp and the enriched liquor.
  • Aromatic and carbohydrate compounds are removed from the reactor as they are solubilised in the solvent mixture, thereby forming the enriched liquor.
  • the catalyst is present within the same tube or vessel.
  • the catalyst can be physically contained so that it remains in the tube, or it can be continuously added and removed as part of the slurry.
  • Hydrogen gas or another hydrogen source needs to be added to the reaction vessel or tube.
  • the catalyst is present in a second vessel or tube, the solvent containing extracted lignin and carbohydrates is added to the second stage after exiting the vessel or tube containing the lignocellulosic biomass. Hydrogen gas or another hydrogen source needs to be added only to the second stage.
  • Multiple continuous reactor systems can operate simultaneously.
  • the continuous reactor systems can operate in parallel, whereby the lignocellulose biomass and the solvent mixture are continuously fed to and the pulp and the enriched liquor are continuously removed from the continuous reactor systems.
  • the enriched liquor obtained from the reactor system 10 can be purified by removal of the carbohydrate- enriched pulp in a separation system 14 by means of filtration, centrifugation, sedimentation or any suitable solid-liquid separation technique, or combinations thereof to provide a pulp stream and a purified liquor stream.
  • the carbohydrate -content of the pulp is higher than the carbohydrate-content of the initial lignocellulosic biomass, therefore, the term carbohydrate-enriched is used.
  • the carbohydrate-content of the obtained pulp is higher than 50 % by mass, for example 65%, or 80%, depending on the carbohydrate content of the used lignocellulosic biomass.
  • the carbohydrate-enriched pulp can be used as a material additive, or can be treated with enzymes, producing for example ethanol or w-butanol.
  • the purified liquor stream is supplied to a separating system 18 that generates at least two streams of the purified liquor stream with equal composition, from which one is re-entered into the reactor system.
  • the amount of the purified liquor stream generated in 18 that is reentered into the reactor system is between 1 % to 99 %.
  • the other 99 % to 1 % of the purified liquor stream generated in separating system 18 is supplied to another separating system 21 that generates a stream comprising the alcohol and the acetate ester and at least one other stream comprising the aromatic and carbohydrate compounds.
  • the purified liquor stream that is supplied to 21 can be separated by distillation, evaporation, membrane separation or any suitable technique that achieves to separate the alcohol and the acetate ester from the purified liquor stream thereby generating at least one other stream comprising the aromatic and carbohydrate compounds, or combinations thereof.
  • the separation system comprises one distillation (or evaporation) step whereby water is at least partially and more preferably by > 99.9 mol% recovered in the stream comprising the aromatic and carbohydrate compounds.
  • the separation system comprises two distillation steps whereby, in a first distillation step, the water is at least partially, and preferably by > 99.9 mol% recovered in a stream comprising the alcohol and the acetate ester, which is then subjected to a second distillation step, whereby a stream comprising the alcohol and the acetate ester, and a stream comprising water are generated.
  • At least 95 mol % and more preferably, at least 99.9 mol % of the alcohol and the acetate ester is recovered in the stream comprising the alcohol and the acetate ester and at least 95 mol% and more preferably, at least 99.9 % of the aromatic and carbohydrate compounds are recovered in the stream comprising the aromatic and carbohydrate compounds.
  • the stream comprising the alcohol and the acetate ester is supplied to another separating system 24 that generates two streams with equal composition from which one is re-entered into the reactor system.
  • the amount of the stream that is re-entered into the reactor system is > 80 % more preferably, > 90% such as 99.9 % of the stream comprising the alcohol and the acetate ester supplied to separating system 24.
  • variables of the process invention 100 described above are interdependent.
  • the following variables, but not limited to those enumerated here, are interdependent: the treatment time, the temperature, the volume of the solvent mixture per mass unit of lignocellulosic biomass, the composition of the solvent mixture, the lignocellulosic biomass characteristics, the amount of the purified liquor stream from separating system 18 re-entered in the reactor system and the amount of the stream comprising the alcohol and the acetate ester from separating system 24 re-entered in the reactor system.
  • the treatment time is preferably between 0.25 to 3 h, such as 1 h
  • the temperature is preferably between 120 °C to 300 °C, such as 220 °C
  • the solvent mixture preferably comprises (z) 0.01 % to 99 % alcohol v/v, such as 45 % v/v, (ii) 0.01 % to 95 % acetate ester v/v, with a side chain identical to the side chain of the alcohol, such as 35 % v/v (Hi) 0.01 % to 95 % water v/v, such as 10 %, and 0.01 % - 95 % v/v of the aromatic and carbohydrate compounds, such as 8 % v/v
  • the volume per kg lignocellulosic biomass is preferably between 2 L/kg to 12 L/kg, such as 10 L/kg, the amount of purified liquor stream from separating system 18 re-entered in the
  • the stream 23 comprising the aromatic and carbohydrate compounds can be purified by a liquid-liquid extraction step using water and an organic solvent, for example, but not limited to, ethyl acetate or dichloromethane, etc. to separate the aromatic compounds from the carbohydrate compounds.
  • the aromatic compounds dissolve more readily in the organic solvent from which they can be separated by for example, but not limited to, membrane separation, evaporation or distillation, or any combination thereof.
  • the recovered organic solvent can then be re-entered to liquid-liquid extraction step.
  • the carbohydrate compounds dissolve more readily in the aqueous phase from which they can be separated by for example, but not limited to, membrane separation, evaporation or distillation, or any combination thereof.
  • the process invention for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds can be further extended.
  • the stream 26 comprising the alcohol and the acetate ester obtained via separation system 24 is supplied to a separation system 27A that generates a stream 28 comprising the alcohol and a stream 29A comprising the acetate ester.
  • the stream 28 is re-entered in the reactor system 10.
  • the separation system 27A can comprise at least one distillation step that generates a stream comprising the alcohol and a stream comprising an azeotropic mixture comprising the alcohol and the acetate ester.
  • the process invention for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds can be extended further to a process that also converts the lignocellulosic biomass into a stream comprising the acetate ester.
  • the stream 26 comprising the alcohol and the acetate ester obtained via separation system 24 is supplied to a separation system 27B that generates at least one stream 28 comprising the alcohol and at least one other stream 29B comprising the acetate ester.
  • the stream 28 is re-entered in the reactor system 10.
  • the separation system 27B comprises at least an azeotropic distillation step that generates a stream comprising the alcohol and a stream comprising the acetate ester.
  • pressure swing distillation is used to break the low-boiling point azeotrope.
  • a third agent is added to the azeotropic distillation step to break the low- boiling point azeotrope.
  • the separation system 27A can comprise at least one distillation step that generates a stream comprising the alcohol and a stream comprising the acetate ester.
  • 95 mol%, more preferably, > 99.5 mol% of the alcohol contained in stream 26 is recovered in the stream comprising the alcohol and > 95 mol%, more preferably, > 99.5 mol% of the acetate ester contained in stream 26 is recovered in the stream comprising the acetate ester.
  • the process invention for converting lignocellulosic biomass into a pulp and a stream containing aromatic and carbohydrate compounds can be extended further to a process that also converts the lignocellulosic biomass into a stream comprising acetic acid.
  • the stream 26 comprising the alcohol and the acetate ester obtained via separation system 24 is supplied to a system 27C that generates at least one stream 28 comprising the alcohol and at least one other stream 29C comprising acetic acid.
  • the stream 28 is reentered in the reactor system 10.
  • the system 27C comprises at least one reactive distillation step where the acetate ester is hydrolysed by reaction with water.
  • the reactive distillation step can be catalysed homogeneously or heterogeneously.
  • process 200C 95 mol%, more preferably, > 99.5 mol% of the alcohol contained in stream 26 is recovered in the stream comprising the alcohol and > 95 mol%, more preferably, > 99.5 mol% of the acetate ester contained in stream 26 is recovered as acetic acid in the stream comprising the acetate acid.
  • Any of 200A, 200B or 200C can be optionally used or used in any combination with invention process 100.
  • Reactor mass balance of lignocellulose fractionation formation of methyl acetate and water
  • Example 2 This example is included to show that acetate ester and water, as well as aromatic and carbohydrate compounds, are formed during lignocellulose fractionation, which are advantageous for the invention process to work, as the solvent mixture comprising the acetate ester and water, as well as the aromatic and carbohydrate compounds, are being enriched therewith in the reactor system (this is made clear by Example 2). More specifically, the mass balance for a reductive catalytic fractionation (RCF) experiment using birch as lignocellulosic biomass, methanol as solvent and Pd/C and hydrogen as the redox catalyst and hydrogen source, respectively, of the catalytic medium is shown here.
  • RCF reductive catalytic fractionation
  • the in- and outputs of the reactor were analyzed using multiple experimental procedures.
  • the reactor content was first filtered to yield a solid pulp, rich in carbohydrates, and, after evaporation of the solvent, a viscous stream named the crude lignin oil comprising the aromatic and carbohydrate compounds.
  • the crude lignin oil was subject to a threefold liquid-liquid extraction with ethyl acetate (EtOAc) and water to produce a viscous stream named, the refined lignin oil comprising the aromatic compounds and, an aqueous solution containing the carbohydrate compounds.
  • EtOAc ethyl acetate
  • the solid pulp composition was determined with a standard total sugar procedure using GC analysis.
  • the lignin content was analyzed by weighing the Klason lignin obtained after filtering the pulp hydrolysate whose UV-absorbance was measured at 240 nm for acidsoluble lignin determination.
  • Acetyl content of the pulp was analyzed by HPLC of the hydrolysate from which the carbohydrates were analyzed by GC as alditol acetates following a derivatization procedure.
  • a similar procedure was followed for the birch compositional analysis.
  • RLO components were derivatized via trimethylsilylation with A-mcthyl-A-(trimcthylsilyl)trifliioroacctamidc. to increase their volatility before GC analysis.
  • FIG. 5 shows an example of the reactor mass balance used in the process simulation, scaled to 100 kg of birch wood (for the sake of simplicity), that was obtained from an extrapolation of the experimental mass balance of the RCF experiment.
  • the birch wood was assumed to have a moisture content of 15 wt% on a wet basis to account for incomplete drying of wood chips commonly used in industrial scale processes compared to wood sawdust ( ⁇ 5 wt%) used in lab-scale experiments.
  • the refined lignin oil is a low-MW oil consisting of aromatic, and more specifically, phenolic monomers and oligomers and has a large selectivity to the 4-w-propanol substituted guaiacyl (11%) and syringyl (31%) monomeric units as shown by its molecular weight distribution ( Figure 6) and gas chromatogram (GC) ( Figure 7).
  • the delignification degree (of 63%) and lignin oil composition signify a successful lignin extraction and depolymerization, and monomer stabilization.
  • the reactor process mass balance was then scaled from the experimental mass balance following a few scale up rules and assumptions. For example, in line with our experimental analysis of the reaction liquor, it was assumed that all the water is released from the wood in RCF.
  • the extractives a diverse group of chemical compounds, though mainly apolar in nature, are only minorly present in the substrate with 2.5 wt%. They were assumed to behave similarly as the aromatic compounds throughout the herein presented biorefmery process, hence end up in the crude lignin oil and eventually, in the refined lignin oil. Ash (0.4 wt%) was assumed to remain in the pulp.
  • the consumption of methanol was estimated by the formation of methyl acetate and methylated sugars and its reformation to CO, CO2 and other gaseous molecules analysed by post-reaction gas phase analysis.
  • methylated C6 sugar derivatives were detected with GC-FID ( Figure 8), they are not shown in this figure given their limited formation in RCF ( ⁇ 0. 1 kg based on 100 kg of wood) as was determined by wood and pulp compositional analyses.
  • the binary interaction parameters were estimated using the UNIFAC correlations which were fit to the NRTL-RK activity coefficient model which was used given the nonideality of the systems under consideration.
  • the molecular structure of the hypothetical components are depicted in Figure 10.
  • Aspen Energy Analyzer ® an energy optimization software tool that is linked to the Aspen HYSYS ® process simulation software, was used for basic heat integration of the process heaters and coolers via pinch point analysis to estimate net heating and cooling requirements of the process.
  • the minimum and maximum temperatures of process streams were confined between 40 °C and 249 °C, respectively, to avoid using refrigerants and fuel oils for cooling and heating, respectively.
  • FIG 12 shows the process flow diagram of a biorefinery process, using RCF as fractionation technique, in which birch wood is converted into a crude lignin oil and a solid pulp.
  • This base process was extended to include a crude lignin oil purification section and a combined heat and power plant for providing the process with energy (these are also shown in Figure 12).
  • the process was designed to convert 150 kt wood y 1 (on a wet basis). It was assumed that the reactor mass balance as obtained for a reaction using solely methanol is constant (see Example 1), although the solvent composition changes according to the simulation, as is demonstrated in Example 3. This assumption, required to create the simulation in the first place, is verified as explained in Example 8 and 9. In what follows is a detailed description of this particular RCF biorefinery process.
  • the solvent mixture is added to a reactor at a ratio of 10 L (at RT) per kg of dry biomass which is comparable to the lab-scale liquor-to-biomass ratio. It is noted that it is advantageous if the solvent stream is being supplemented with fresh methanol to account for solvent losses in the reaction and downstream processing and ensure a constant volumetric flow rate (at RT).
  • hydrogen is fed to the reactor at a rate of 0.05 kg hydrogen per kg of dry biomass ( ⁇ conform the loading of hydrogen in the lab reactor at 30 bar, at RT), and make-up hydrogen is added to a recycle stream to account for hydrogen consumption during the wood treatment in the reactor.
  • the reactor inlet streams viz. , the fresh wood, the solvents and hydrogen are conditioned to 220°C and 90 bar before reactor entry.
  • the gases and vapors are removed from the reactor via an in-line flash at high temperature and pressure, and are subsequently cooled and fed to a flash tank to separate the gases from the vapors viz. , methanol, methyl acetate and some water, which are recovered as a liquid.
  • Excess hydrogen is purified from the gaseous stream containing some short-chain alkanes, CO and CO2 by pressure swing adsorption (PSA), which was modelled by a component split, and is recycled to the reactor section.
  • PSA pressure swing adsorption
  • the resulting purified liquor stream contains methanol, methyl acetate, water and crude lignin oil, and is partially fed to the crude oil distillation column.
  • This column was designed to recover 99.9% of the inlet methanol (the light key component) in the overheads stream, without entrainment of water (the heavy key component).
  • Methyl acetate, having a lower boiling-point than methanol at the column operational pressure (2 bar) is always recuperated in this overheads stream as well.
  • the bottoms stream of the column consists of water and the crude lignin oil.
  • Methanol and methyl acetate of the overheads are used in a pulp washing step before being mixed with the flash tank condensate (mix 1), whilst the bottoms stream is fed to the crude lignin oil purification section.
  • the liquid stream Prior to the crude oil distillation, the liquid stream can be split at a predefined ratio (split 1) into two streams. Only one stream is fed to the column whilst the other is pressurized and mixed (mix 2) with the condensate recycle stream.
  • the resulting liquid stream - the solvent recycle - contains methanol, methyl acetate, water, crude lignin oil, and some acetic acid and is redirected to the reactor section where fresh methanol is added to maintain the set volumetric flow rate of 10 L solvent (at RT) per kg dry wood.
  • the liquid stream obtained in mix 2 can be purged (dotted line - split 2) prior to mixing (mix 2), to control the solvent composition, and in particular, the enrichment of methyl acetate in the solvent recycle stream.
  • the basis of this process was extended with a crude oil purification section to yield a refined lignin oil, comprising the lignin-derived phenolics, and an aqueous solution, comprising the methylated carbohydrate compounds, mainly originating from the birch hemicellulose.
  • the crude lignin oil is further purified by liquid-liquid extraction with ethyl acetate and water resulting in an organic phase, enriched with the lignin oil aromatics, and an aqueous phase, containing the carbohydrate derivatives.
  • the amount of water and ethyl acetate used in the liquid-liquid extraction was set to 1.1 kg of each per kg of crude lignin oil to ensure a good separation.
  • the purge stream comprising methanol and methyl acetate does not necessarily need to be supplied to the CHP plant but can be valorized in different ways. This is possible as the methyl acetate accumulates and becomes concentrated in the solvent recycle streams, thus also, in the purge stream from split 2. This extension to the process is also shown on the schematic overview of the process in Figure 12.
  • Figure 13 shows the solvent composition for four cases with conceptually different solvent recycling strategies in the RCF biorefmery.
  • the solvent mixture solely consists of methanol (Figure 13 - No Recycle).
  • the solvent mixture contains mostly methanol (90 v%), some water (3 v%) and 6 v% crude lignin oil, but only a negligible amount of methyl acetate ( ⁇ 1 wt%) ( Figure 13 - Liquor Recycle Only). Thus, methyl acetate is not able to concentrate in the solvent mixture in this case.
  • the solvent mixture comprises methanol (73 v%), methyl acetate (25 v%) and water (2 v%), but no crude lignin oil (Figure 13 - Solvent Recycle only). It is noted to be advantageous if both streams are re-entered to guarantee that all 4 solvent constituents viz., methanol, methyl acetate, water and crude lignin oil are present in the solvent mixture ( Figure 13 - Both Recycle) .
  • the solvent mixture contains 58 v% methanol, 26 v% methyl acetate, 8 v% water and 7 v% crude lignin oil.
  • This example is included to show that the relative amount of the purified liquor stream obtained after the solid-liquid separation that is re-entered into the reactor system can be modified to control the solvent composition and volumetric flow at reaction conditions of the solvent mixture.
  • This is shown for the RCF biorefinery process introduced in Example 2 for which the composition of the solvent mixture is modelled when the ratio by which the purified liquor stream is split between a stream that is supplied to the crude oil distillation and a stream that is re-entered into the reactor (split 1 in Figure 12) is systematically varied.
  • This ratio is hereafter referred to as the distillation split ratio.
  • a distillation split ratio of 75% means that 75% of the purified liquor stream supplied to split 1 is re-entered into the reactor whereas 25% is fed to the crude oil distillation column.
  • the main goal of this liquid split is to decrease the load on the crude oil distillation column. It can be anticipated that, along with the recycling of methanol and methyl acetate, the energy requirements of the process can be drastically reduced in this way, by reducing the evaporation volumes of the solvents
  • the liquid split affects the mass flow and composition of multiple process streams, including the inlet solvent stream of the reactor and the purge stream to the CHP. Its impact on the process operation was therefore investigated using the steady-state process simulation as described in Example 2. Here it was assumed that the reactor mass balance (Figure 5) remained unaltered. This important assumption was verified as is described in Example 8 and 9. The purge ratio (0.1 %, split 2) and the distillation column design specifications were kept constant throughout these simulations.
  • the methanol solvent stream is primarily enriched with methyl acetate (30 wt%) along with some water (2 wt%) originating from the flash tank liquid. This corresponds to case Liquor Recycle only in previous Counter Example 3.
  • the concentration of the crude lignin oil and water increase at higher split ratios, though only minorly.
  • the solvent contains 9 wt% water and 8 wt% crude lignin oil at a split ratio of 75%. This corresponds to case Both Recycle in previous counter example 3. Only at the highest split ratio (e.g., 90%), the solvent stream becomes highly concentrated with water (20 wt%) and crude lignin oil (21 wt%).
  • the distillation split ratio also affects the volumetric flow of the solvent at the fixed reactor conditions of 220 °C and 90 bar.
  • the flow rate decreases with an increasing split ratio as less volatile water and crude lignin oil become more concentrated in the solvent, resulting in a smaller volumetric expansion (-20% at 75% split and - 25% at 90% split, compared to 0% split) at reaction temperature ( Figure 14). This implies that the reactor can be smaller, especially at higher split ratios, which is an added advantage of reducing the distillation load.
  • This example is included to show that by increasing the relative amount of the purified liquor stream obtained after the solid-liquid separation that is re-entered into the reactor system the energy demand, the consumption of utilities, and, the CO2 emissions of the process can be reduced.
  • This is shown for the RCF biorefinery process introduced in Example 2 for which the process mass and energy balances are re-evaluated when the ratio by which the purified liquor stream is split between a stream that is supplied to the crude oil distillation and a stream that is re-entered into the reactor (split 1 in Figure 12) is systematically varied.
  • the altering mass and energy balances of the RCF biorefinery at a distillation split ratio of 0, 50 and 75% show that the process requires less energy at a reduced load on the crude distillation column (Table 4).
  • the intake of hydrogen for the production of steam decreases by 80% at a high distillation split ratio of 75% compared to 0%, from 2308 kg.h 1 to 487 kg.h 1 .
  • the electric power, mainly required for the cooling water pump around shows a similar trend. Its consumption decreases by 85% for a distillation split ratio of 75% compared to 0%, from 2100 kW to 328 kW.
  • a 3-fold decrease in water consumption at a high liquid split of 75% compared to no liquid split is also illustrative for the reduced cooling demands.
  • the need for fewer energy at high distillation split is also exemplified by the ratio of the total energy input and the wood heating value.
  • the energy input without a liquid split is equivalent to a high 98.2% of the wood heating value. However, this ratio decreases to 48.6% and to 23.2% at split ratios of 50 and 75%, respectively.
  • This example is included to show that by increasing the relative amount of the purified liquor stream obtained after the solid-liquid separation that is re-entered into the reactor system the operational and capital expenses and the minimum selling price of the aromatic compounds obtained from the lignin of the lignocellulosic biomass can be reduced.
  • This is shown for the RCF biorefinery process introduced in Example 2 for which the process economics are re-evaluated when the ratio by which the purified liquor stream is split between a stream that is supplied to the crude oil distillation and a stream that is re-entered into the reactor (split 1 in Figure 12) is systematically varied.
  • the capital expenditures (CAPEX) were estimated using the factorial cost estimation method, which is a method commonly employed for cost estimation of chemical production processes. Sizing parameters of the reactor and all other unit operations were (in)directly obtained from the Aspen HY SYS simulation and the sizing parameters of the heat exchangers were estimated by the Aspen Energy Analyzer. Reactors were modelled as jacket agitated vessels based on their volume which was estimated from the volumetric flowrate of the reactor outlet at reaction temperature and the reactor residence time. Stainless steel material ss316 was used for the reactor section, crude oil distillation and recycle system, but not for the crude oil purification unit operations.
  • Costs of the CHP were modelled using an overnight capital cost of 950 €.kW -1 for the gas turbine and the steam boiler cost equation using the factorials method. Costs were escalated using appropriate cost escalation indices and converted to European pricing by multiplication with a European averaged location factor of 1.11 and a currency rate of 0.9 €.$ -1 .
  • Table 5 A list with detailed economic parameters is presented Table 5.
  • Operational expenditure (OPEX) were determined by the variable costs of the raw materials, consumables, utilities which were obtained from the process simulation and CHP calculations and the fixed costs of production (i.e., salaries, overheads, property tax, environmental costs, etc.). Pricing of the raw materials, consumables, utilities and products are shown in Table 6.
  • Wood feedstock price was set to 158 €.t -1 as previously estimated by Liao et al. Pulp and aqueous sugars are sold for a 400 €.t -1 price, following an average sugar price.
  • the minimum selling price was solved for the net present value (NPV) of the project to be zero using a weighted average cost of capital of 15%.
  • the project life time was set to 20 years and a capital depreciation period of 10 years was used in a straight line depreciation procedure.
  • the volume for each ofthe four reactors declines from 391 to 289 m 3 between a distillation split ratio of 0 and 90%, respectively. Accordingly, the reactor costs decrease from 98 to 77 M €. With a share of 55 to 75%, the reactor costs contribute by far the most to the total capital expenditure which, in total, decreases from 176 to 103 M €, i.e., a 59% reduction.
  • MSP-RLO refined lignin oil
  • Figure 16 We marked the selling price of benzene, phenol and bisphenol A (BPA) in Figure 16 to position the lignin oil within the market of aromatic and phenolic petrochemicals, where it should become competitive as a bio-based alternative in the long term.
  • BPA bisphenol A
  • the MSP-RLO coincides with the BPA selling price but still exceeds the selling price of phenol (1100 €.t -1 ) and benzene (400 €.t -1 ).
  • the added-value of the lignin oil mixture should be comparable to pure BPA. This is rather unlikely as until now, the lignin oil needs additional processing to yield monomer derived bisphenols or oligomers that are equivalent to BPA and there is no margin for this at the current pricing.
  • the MSP-RLO decreases to below 1000 €.t -1 , in between the phenol and benzene selling prices.
  • This MSP agrees better with its role as a platform for phenolics as it allows for additional downstream processing and upgrading to chemicals equivalent to phenol, bisphenol A and others, which have higher prices. This signifies that the operation of the refinery can be economically viable.
  • This example is included to show that by increasing the relative amount of the purified liquor stream obtained after the solid-liquid separation that is re-entered into the reactor system, the CO2 footprint of the process can be reduced.
  • This is shown for the RCF biorefinery process introduced in Example 2 for which the global warming potential of the lignin-derived aromatics (GWP) is re-evaluated using life cycle analysis (LCA) when the ratio by which the purified liquor stream is split between a stream that is supplied to the crude oil distillation and a stream that is re-entered into the reactor (split 1 in Figure 12) is systematically varied.
  • LCA life cycle analysis
  • FIG. 17 A diagram ofthe LCA cradle-to-gate system boundary can be found in Figure 17.
  • Process in- and outputs of the were simulated with the Aspen HYSYS process simulation.
  • Life cycle inventories of the background technologies and production processes for the process in- and outputs were obtained from Ecoinvent v3.8 and Thinkstep Gabi professional database to determine their environmental impact.
  • the production processes and corresponding GWP values for each of the in- and outputs are listed in Table 7. Biogenic carbon uptake and emission were considered for those biogenic carbon streams, for which appropriate characterization factors could be estimated for biogenic carbon accounting in LCA.
  • process CO2 emissions from biogenic origin like the acetyl combustion in the CHP were accounted for in the GWP calculations by using a characterization factor of 0.2, assuming a birch rotation time of 50 years, and biogenic carbon life time of 0 years as it is directly combusted at the process level.
  • Biogenic carbon that ends up in the products viz., refined lignin oil, pulp and aqueous sugars
  • Economic allocation based on product and by-product revenues was used to assign CO2 emissions to the refined lignin oil.
  • GWP values were calculated for a 100-year time scale and expressed in kg of CO2 equivalent.
  • the GWP-RLO is calculated at varying distillation split ratio by leveraging the process mass and energy balances that are described in Example 4 to the life cycle inventory of the LCA.
  • the GWP decreases from 1.21 to 0.85 kgCCE.kg RLO 1 between a split ratio of 0 and 90% consistent with the reduced energy requirements at lower distillation load as described in Example 4 ( Figure 18). This is exemplified by a decreasing footprint of hydrogen (0.4 - 0.02 kgCCF.kg RLO 1 ).
  • the high impact of hydrogen at low split ratio suggests that its impact on the GWP is still significant, even when produced in a sustainable way, in this case, via wind-powered electrolysis.
  • the CO2 footprint of the wood feedstock remains constant (0.5 kgCO2.kg RLO 1 ), but is positive, as it solely represents the CO2 emissions associated with harvesting and processing of birch trees to wood chips.
  • the GWP of the lignin oil is lower than the GWP of bisphenol A (2.32 kgCO2.kg -1 ), benzene (1.93 kgCO2.kg -1 ) and phenol (1.75 kgCO2.kg -1 ) ( Figure 18)
  • This margin is expected to be large enough for the GWP of lignin oil derived products to increase in downstream upgrading processes before it exceeds the GWP of phenol, benzene and bisphenol A. This signifies that the process can operate in a more sustainable way than conventional processes.
  • Example 8 This example is included to show that solvent mixtures of the alcohol, the acetate ester, water and the aromatic and carbohydrate compounds are suitable for and, even enhance the fractionation of lignocellulosic biomass, which also validates the assumptions made in the process simulations, as is described in Examples 2 to 4.
  • the results of the pulp compositional analysis of Example 8 show that more lignin is extracted from birch in RCF with a solvent mixture of methanol, methyl acetate, water and crude lignin oil, compared to pure methanol.
  • the lignin oil was analyzed after removal of carbohydrates. Similar experimental procedures were applied as described in Example 1.
  • Figure 20 depicts the yield of the syringyl-type monomeric units relative to the birch protolignin (i.e., the S-monomer yield in wt%).
  • the S-monomer yield amounts 20% and 21% for the solvent mixtures comprising methanol, methyl acetate and water (MeOH + MA/H2O) and methanol, methyl acetate, water and crude lignin oil (MeOH + MA/H 2 O/CLO), respectively, thereby slightly exceeding the S-monomer yield of the reaction with pure methanol (19%).
  • the reaction of hardwood birch with methanol as solvent and a Pd/C catalyst is highly selective to 4-w-propanolsyringol (POHS) with a limited formation of 4-n- propylsyringol (PS) and has a comparable monomer selectivity of 44% as shown on Figure 20A, in which the monomer composition of the entire refined lignin oil is depicted.
  • POHS 4-w-propanolsyringol
  • PS 4-n- propylsyringol
  • methyl acetate induces the formation of 3-(4-hydroxy-3,5-dimethoxyphenyl)propylacetate, hereafter referred to as 4-w-propylacctatcsyringol (POAcS), presumably by a partial acetylation of the propanol side chain of POHS, as indicated by a lower yield the RCF reactions with a solvent mixture containing methyl acetate compared to the pure methanol reaction.
  • Acetylation of the propanol side chain also occurs with the guaiacyl-type (G-type) monomers.
  • the refined lignin oils obtained with the applied solvent mixtures contain 4-w-propanolguaiacol (POHG) and 4-w-propylacctatcguaiacol (POAcG) ( Figure 21 A and Figure 22).
  • POHG 4-w-propanolguaiacol
  • POAcG 4-w-propylacctatcguaiacol
  • the spruce lignin oil has been enriched with birch lignin oil given the presence of S-type monomers and as indicated by an intermediate monomer yield of the oil (33%) between those of the spruce (30%), and birch (43%) lignin oil obtained with pure methanol RCF.
  • the lignin oil monomer yield of the resulting lignin oil is closer to the monomer yield of the spruce than the birch oil, as could have been expected in advance.
  • the average molecular weights of the lignin oil obtained for reaction with methanol and methyl acetate increase compared to the base case (from 356 to 377 g.mol 1 and 596 to 634 g.mol 1 ), which is likely induced by a partial acetylation of 4-w-propanol side chains.
  • M n and M w have increased, it can be inferred that lignin monomers as well as dimers and oligomers are prone to acetylation, which is plausible, as oligomers have propanol side chains, and usually more than one - as shown by detailed molecular analysis of dimers and trimers by Van Aelst et al. and Dao Thi et al.
  • a larger extraction of high MW-lignin as indicated by a high birch delignification and/or a hindered reductive stabilization enabling lignin recondensation might also have increased the average molecular weights of this lignin oil.
  • These counteracting factors decreasing (e.g., low-MW birch lignin oil enriching the high-MW spruce lignin oil) and increasing (e.g., acetylation, high-MW lignin extraction, lignin recondensation) the lignin oil MW can explain these shifts.
  • This example is included to show that the fractionation of lignocellulosic biomass can be performed at a decreased reaction time and/or temperature when using the solvent mixture of the alcohol, the acetate ester, water and the aromatic and carbohydrate compounds.
  • a solvent mixture comprising methanol, methyl acetate, water and crude lignin oi.
  • Reducing the reaction temperature to 200 °C has a similar effect as halving the reactor residence time: fewer lignin is extracted (yet, the delignification is with 72% still higher than the reaction with pure methanol), the S-monomer yield ( 11 %) is lower and the monomer composition of the refined lignin oil is dominated by the spruce-derived G-type monomers.
  • the reaction temperature and reactor residence time are halved at the same time, the applied solvent mixture do not work properly as indicated by the same metrics.
  • the molecular weight distribution of the oils ( Figure 23) and corresponding averaged molecular weights do not differ much between the various conditions tested here.
  • the M n and M w values have increased by ⁇ 38 and ⁇ 130 g.mol 1 compared to spruce lignin oil, to ⁇ 445 and ⁇ 770 g.mol 1 , respectively, compared to spruce lignin oil, implying that some acetylation has occurred in all instances (Table 8). However, this can also be explained by other factors as outlined above, which are temperature and time dependent as well.
  • This example is included to show that the economics and carbon footprint of the invention process are improved at a decreased the reaction time or temperature in the reactor by using the solvent mixture of the alcohol, the acetate ester, water and the aromatic and carbohydrate compounds.
  • the MSP-RLO decreases for the case using the solvent mixture mimicking a high distillation split ratio for a reactor residence time of 2 h and a reaction temperature of 220 °C as the lignin oil yield was estimated to be 49% higher relative to the pure methanol (Table 9).
  • the MSP for the mixture declines from 1238 to 831 €.t -1 .
  • the GWP-RLO decreases from 0.90 to 0.76 kgCO2.kg" 1 as the same amount of CO2 emissions are allocated over larger lignin oil revenues under economic allocation.
  • the MSP-RLO drops to 653 €.t -1 .
  • This example is included to show that the energy requirements of the process introduced in Example 2 decrease when both the solvent recycle stream, comprising the alcohol and the acetate ester, and the liquor recycle stream, comprising also the aromatic and carbohydrate compounds (i.e., the crude lignin oil) and water, are re-entered in the reactor system compared to the process where only the solvent recycle stream is re-entered in the reactor system, but not the liquor recycle stream.
  • this Counter Example 12 is comparable with Counter Example 3 where the impact of liquor recycling on the solvent composition is discussed.
  • the RCF biorefinery process converts birch lignocellulosic biomass, the alcohol is methanol, and the acetate ester is methyl acetate.
  • the amount of hydrogen fuel that needs to be combusted in the CHP decreases from 2297 kg/h to 476 kg/ ( Figure 25).
  • the cooling water intake necessary to provide the cooling capacity to the process, also diminishes, from 123733 kg/h to 37305 kg/h ( Figure 26).
  • This example is included to show that by using a solvent mixture, obtained by re-entering both the solvent and liquor recycle streams in the reactor system, in the lignocellulose fractionation step results in a higher delignification thus a larger lignin oil production, and a purer pulp enriched with more carbohydrates compared to a lignocellulose fractionation step in which the solvent mixture obtained by solely re-entering the solvent recycling stream in the reactor system is used.
  • RCF experiments were conducted with the solvent mixtures as shown in Figure 13 and as discussed in Counter Example 3. The experimental procedure of RCF experiment is described in Example 1. In this example, the RCF reactions are conducted with birch lignocellulosic biomass, the alcohol is methanol, and the acetate ester is methyl acetate.
  • the composition of the pulps obtained after the various RCF reactions are shown in Figure 27 on the left axis and compared to the composition of birch, used here as lignocellulosic biomass.
  • the delignification extent i.e., the amount of native lignin removed from birch, is also shown (on the right axis) ( Figure 27).
  • the carbohydrates are enriched in the pulp after the RCF reaction as is shown by the pulp composition.
  • the amount of lignin present in the pulp is lowest (3.52 wt%) for the “both solvent and liquor recycle’” reaction compared to the lignin content of 7.34 and 12.60 wt% for the “solvent recycle only” and “no recycle” reactions, respectively.
  • This example is included to show that by re-entering a part of the liquor recycle stream in the reactor system - irrespective of the amount (i. e. , irrespective of the distillation split ratio or the liquor recycling (%)) - along with the solvent recycle stream, the energy requirements of the process introduced in Example 2 are reduced.
  • This example is also included to show that by increasing the recycling rate of the liquor recycle stream when both the solvent and liquor recycle streams are re-entered in the reactor system, the process energy requirements decline.
  • the RCF biorefmery process converts birch lignocellulosic biomass, the alcohol is methanol, and the acetate ester is methyl acetate.
  • the required hydrogen fuel intake ( Figure 30) and the cooling water consumption (Figure 31) decrease from 2297 to 10 kg/h and 123733 to 16199 kg/h, respectively, between a 0% and 90% liquor recycling, respectively.
  • the required hydrogen fuel intake ( Figure 30) and the cooling water consumption (Figure 31) decrease from 2297 to 10 kg/h and 123733 to 16199 kg/h, respectively, between a 0% and 90% liquor recycling, respectively.
  • This is example is included to show that the fractionation step used for converting the lignocellulosic biomass works when using solvent mixtures, obtained by re-entering the solvent recycle stream and various amounts of the liquor recycle stream into the reactor system.
  • This example is also included to show that the delignification extent, i.e., the amount of the native lignin that is removed from the lignocellulosic biomass in the fractionation step, increases when using solvent mixtures obtained by reentering the solvent recycle stream and various amounts of the liquor recycle stream in the reactor system.
  • the composition of the pulps obtained after the various RCF reactions are shown in Figure 31 on the left axis and compared to the composition of birch, used here as lignocellulosic biomass.
  • the delignification extent i.e., the amount of native lignin removed from birch, is also shown (on the right axis) in Figure 31.
  • the carbohydrates are enriched in the pulp by more than 82 % of the pulp weight after the RCF reaction and the carbohydrate fraction of the pulp is larger for all cases with liquor recycling (between 88 - 93 wt%) except for when a liquor recycling of 90% is used.
  • the carbohydrate content of the pulp is somewhat lower (82 wt%), which still signifies a successful pulping when compared to the carbohydrate content (65 wt%) of the birch lignocellulosic biomass (see Figure 31).
  • the delignification extent confirms these findings. More than 84 wt% of the native lignin is removed from the birch lignocellulosic biomass in all “liquor recycling” cases. The delignification extent is even higher for the case with a 90% liquor recycling compared to the case where only the solvent is recycled and re-entered in the reactor system (80.3 wt% for “solvent recycle only”).
  • Figure 32 shows that monomer formation and stabilization step has occurred in the RCF step despite the presence of the aromatic and carbohydrate compounds (i.e., crude lignin oil) in the reaction mixture.
  • Syringyl type monomers S-monomers
  • Figure 32A are formed in the conversion step and are enriched in the spruce crude lignin oil, which was originally added to mimic the solvent mixtures at a liquor recycling above 0% as is also explained in Example 8 ( Figure 32B).
  • the GC- spectra of the refined lignin oils in Figure 33 show that S-monomers are formed in the fractionation steps in which spruce lignin oil (Spruce - MeOH) is already added.
  • the typical GPC spectra in Figure 35 and the low number average ( ⁇ 500 g/mol) and weight average ( ⁇ 900 g/mol) molecular weights of the lignin oils in Table 10 show that the lignin has successfully depolymerized to monomers, dimers, and low molecular weight oligomers.
  • Figure 34 shows that carbohydrates are formed in these reactions as well.
  • This example is included to show that acetate ester and water, as well as aromatic and carbohydrate compounds, are formed during lignocellulose fractionation using a softwood lignocellulosic biomass.
  • the formation of these compounds in the fractionation step are essential for the invention process to work, as the solvent mixture comprising the acetate ester and water as well as the aromatic and carbohydrate compounds are being enriched therewith in the reactor system (as is made clear in Example 2). More specifically, the mass balance for an RCF experiment using spruce as lignocellulosic biomass, methanol as solvent and Pd/C and hydrogen as the redox catalyst and hydrogen source, respectively, of the catalytic medium is shown here.
  • Example 2 The same experimental procedures extensively explained in Example 1 are used in this example to obtain the reactor mass balance for the RCF reaction with the spruce lignocellulosic biomass.
  • 100 kg of wood on a wet basis 70.3 kg pulp, 14.2 kg crude lignin oil comprising phenolics and methylated carbohydrates, 2. 1 kg methyl acetate and 15 kg water are produced, and 1.6 kg of methanol is consumed forming methyl acetate (2. 1 kg) and methylated carbohydrates (4.0 kg), by deacetylation and solvolytic depolymerization of (hemi-)cellulose, respectively (Figure 36). Hydrogen consumption (0.05 kg) and methanol reforming (1.2 kg) are not shown on Figure 36 for the sake of clarity.
  • FIG. 37 shows the molecular weight distribution of the spruce lignin oil following an RCF reaction.
  • This GPC chromatogram shows that lignin-derived monomers, dimers, and low molecular weight oligomers have been formed in the fractionation step.
  • the GC chromatogram in Figure 38 shows the formation of exclusively guaiacyl-type monomers (G-type monomers, i.e., with only one methoxy group on the phenolic ring).
  • Figure 39 shows the GC -chromatogram of the dissolved carbohydrates, originating from the spruce (hemicellulose.
  • Figure 40B shows GC -chromatogram of the reaction liquor after the fractionation experiment. It signifies the successful formation of methyl acetate by reaction of the hemicellulose acetyl groups with the solvent methanol.
  • the standards for methyl acetate in methanol at various concentrations are shown in Figure 40A for comparison.
  • Spruce as the lignocellulosic biomass the operation of the process with versus without the liquor recycle stream
  • This example is included to show that it is necessary that both, a part of the purified liquor recycle stream comprising the solvent mixture and solubilized aromatic and carbohydrate compounds and, a part of the solvent recycle stream comprising the alcohol and the acetate ester obtained after separation from the aromatic and carbohydrate compounds, are re-entered in the reactor system to obtain the unique solvent mixtures for contacting the lignocellulosic biomass with.
  • This is shown with the process simulation of the RCF biorefinery introduced in Example 2 in which spruce is used as the lignocellulosic biomass and the alcohol is methanol and the acetate ester is methyl acetate.
  • Figure 41 shows the solvent composition for four cases with conceptually different solvent recycling strategies in the RCF biorefinery when spruce is used as the lignocellulosic biomass.
  • the solvent mixture solely consists of methanol ( Figure 41 - No Recycle).
  • the solvent mixture contains mostly methanol (88 v%), some water (4 v%) and 8 v% crude lignin oil, but only a negligible amount of methyl acetate ( ⁇ 0.5 wt%) ( Figure 41 - Liquor Recycle Only). Thus, methyl acetate is not able to concentrate in the solvent mixture in this case.
  • the solvent mixture comprises methanol (89 v%), methyl acetate (10 v%) and water (1 v%), but no crude lignin oil (Figure 41- Solvent Recycle only). It is noted that both streams must be re-entered in the reactor system to guarantee that all 4 solvent constituents viz. , methanol, methyl acetate, water and crude lignin oil are present in the solvent mixture ( Figure 41 - Both Solvent and Liquor Recycle).
  • the solvent mixture contains 76 v% methanol, 9 v% methyl acetate, 9 v% water and 6 v% crude lignin oil.
  • This example is included to show that the energy requirements of the process introduced in Example 2 decrease when both the solvent and liquor recycling streams are re-entered in the reactor system compared to the process where only the solvent recycle stream, containing the alcohol and acetate ester, is re-entered in the reactor system, but not the liquor recycle stream which also contains the aromatic and carbohydrate compounds (i.e., the crude lignin oil) and water.
  • the process converts spruce lignocellulosic biomass, the alcohol is methanol, and the acetate ester is methyl acetate.
  • Spruce as the lignocellulosic biomass improved delignification and pulp composition with versus without the liquor recycle stream
  • This example is included to show that by using a solvent mixture, obtained by re-entering both the solvent and liquor recycle streams in the reactor system, in the lignocellulose fractionation step results in a higher delignification thus a larger lignin oil production, and a purer pulp enriched with more carbohydrates compared to a lignocellulose fractionation step in which the solvent mixture, obtained by solely re-entering the solvent recycling stream in the reactor system, is used.
  • This example specifically shows that this also applies to a softwood feedstock, here, spruce.
  • RCF experiments were conducted using the solvent mixtures shown in Figure 41 as discussed in Counter Example 17. The experimental procedure of the RCF experiment is described in Example 1 . In this example, the RCF reactions are conducted with spruce lignocellulosic biomass, the alcohol is methanol, and the acetate ester is methyl acetate.
  • the amount of lignin present in the pulp is lower (16.3 wt%) for the “both solvent and liquor recycle” reaction compared to the lignin content of 19.6 and 20.1 wt% for the “solvent recycle only” and “no recycle” reactions, respectively.
  • the added benefit of re-entering part of the liquor recycling stream into the reactor system is that the solvent mixture obtained thereby can remove more lignin from the spruce lignocellulosic biomass than when using a solvent mixture that is obtained by only re-entering the solvent recycle stream in the reactor system.
  • This example is included to show that acetate ester and water, as well as aromatic and carbohydrate compounds, are formed during lignocellulose fractionation when using ethanol as the alcohol.
  • the formation of these compounds in the fractionation step are essential for the invention process to work, as the solvent mixture comprising the acetate ester and water as well as the aromatic and carbohydrate compounds are being enriched therewith in the reactor systems (as will be made clear by Example 21). More specifically, the mass balance for an RCF experiment using birch as lignocellulosic biomass, ethanol as solvent and Pd/C and hydrogen as the redox catalyst and hydrogen source, respectively, of the catalytic medium is shown here.
  • Example 2 The same experimental procedures as extensively explained in Example 1 are used in this example to obtain the reactor mass balance for the RCF reaction with birch lignocellulosic biomass and ethanol as the alcohol.
  • 100 kg of wood on a wet basis 62.8 kg pulp, 22.7 kg crude lignin oil comprising phenolics and ethylated carbohydrates, 3.4 kg ethyl acetate and 15 kg water are produced, and 4.0 kg of ethanol is consumed forming ethyl acetate (3.4 kg) and ethylated carbohydrates (9.3 kg), by deacetylation and solvolytic depolymerization of (hemi-)cellulose, respectively.
  • FIG. 50 shows the molecular weight distribution of the birch lignin oil following an RCF reaction with ethanol.
  • This GPC chromatogram shows that lignin-derived monomers, dimers, and low molecular weight oligomers have been formed in the fractionation step.
  • the GC chromatogram in Figure 51 shows the formation of guaiacyl -type and syringyl-type monomers formed in the depolymerization and subsequent stabilization of lignin fragments.
  • Figure 52 shows the GC-chromatogram of the dissolved carbohydrates, originating from the birch (hemi-)cellulose.
  • Figure 53B shows GC-chromatogram of the reaction liquor after the fractionation experiment. It signifies the successful formation of ethyl acetate by reaction of the hemicellulose acetyl groups with the solvent ethanol.
  • the standards for ethyl acetate in ethanol at various concentrations are shown in Figure 53A for comparison.
  • the process configuration in this example is similar as the process introduced in Example 2 except for the separation step to recover the solvent recycle stream which contains the alcohol and the acetate ester, here, ethanol and ethyl acetate, from the purified liquor obtained by a solid-liquid separation of the reaction liquor.
  • a two-step distillation process is used in this case with ethanol and ethyl acetate (see Figure 54).
  • the first distillation step produces a stream comprising ethanol and ethyl acetate whilst the second distillation step recovers the ethanol that has remained in the bottoms stream of the first column.
  • the top stream of the first column is used in a pulp washing step, and subsequently mixed with the top stream of the second column to form the solvent recycle stream. This stream is re-entered in the reactor system along with the flash condensate and the liquor recycle stream.
  • This example is included to show that it is necessary that both, a part of the purified liquor recycle stream comprising the solvent mixture and solubilized aromatic and carbohydrate compounds and, a part of the solvent recycle stream comprising the alcohol and the acetate ester obtained after separation from the aromatic and carbohydrate compounds, are re-entered in the reactor system to obtain the unique solvent mixtures for contacting the lignocellulosic biomass with.
  • This is shown with the process simulation of the RCF biorefinery introduced in Example 21 in which birch is used as the lignocellulosic biomass and the alcohol is ethanol and the acetate ester is ethyl acetate.
  • Figure 55 shows the solvent composition for four cases with conceptually different solvent recycling strategies in the RCF biorefinery when birch is used as the lignocellulosic biomass and the alcohol is ethanol.
  • the solvent mixture solely consists of ethanol ( Figure 55 - No Recycle).
  • the solvent mixture contains mostly ethanol (89 v%), some water (3 v%) and 8 v% crude lignin oil, but only a negligible amount of ethyl acetate ( ⁇ 0.5 wt%) ( Figure 55 - Liquor Recycle Only).
  • ethyl acetate is not able to concentrate in the solvent mixture in this case.
  • the solvent mixture comprises ethanol (91 v%), ethyl acetate (3 v%) and water (5 v%), but no crude lignin oil (Figure 55 - Solvent Recycle only). It is noted that both streams must be re-entered in the reactor system to guarantee that all 4 solvent constituents viz., ethanol, ethyl acetate, water and crude lignin oil are present in the solvent mixture ( Figure 55 - Both Solvent and Liquor Recycle).
  • the solvent mixture contains 73 v% ethanol, 6 v% ethyl acetate, 10 v% water and 9 v% crude lignin oil.
  • This example is included to show that the energy requirements of the process introduced in Example 21 decrease when both the solvent and liquor recycling streams are re-entered in the reactor system compared to the process where only the solvent recycle stream, containing the alcohol and acetate ester, is re-entered in the reactor system, but not the liquor recycling stream which also contains the aromatic and carbohydrate compounds (z. e. , the crude lignin oil) and water.
  • the process converts birch lignocellulosic biomass, the alcohol is ethanol, and the acetate ester is ethyl acetate.
  • the amount of hydrogen fuel that needs to be combusted in the CHP decreases from 5082 kg/h to 943 kg/h ( Figure 57).
  • the cooling water intake, necessary to provide the cooling capacity to the process also diminishes, from 299851 kg/h to 68029 kg/h ( Figure 58).
  • This example specifically shows that the findings for methanol as the alcohol (see Counter Example 12) are also applicable when ethanol is used as the alcohol.
  • Ethanol as the alcohol improved delignification and pulp composition with versus without the liquor recycle stream
  • This example is included to show that by using a solvent mixture, obtained by re-entering both the solvent and liquor recycle streams in the reactor system, in the lignocellulose fractionation step results in a higher delignification thus a larger lignin oil production, and a purer pulp enriched with more carbohydrates compared to a lignocellulose fractionation step in which the solvent mixture, obtained by solely re-entering the solvent recycling stream in the reactor system, is used.
  • This example specifically shows that this also applies to solvent mixtures in which ethanol is the alcohol and ethyl acetate is the acetate ester.
  • RCF experiments were conducted using the solvent mixtures shown in Figure 55 as discussed in Counter Example 22. The experimental procedure of the RCF experiment is described in Example 1. In this example, the RCF reactions are conducted with birch lignocellulosic biomass, the alcohol is ethanol, and the acetate ester is ethyl acetate.
  • the composition of the pulps obtained after the various RCF reactions are shown in Figure 59 on the left axis and compared to the composition of birch, used here as lignocellulosic biomass.
  • the delignification extent i.e., the amount of native lignin removed from birch, is also shown (on the right axis) ( Figure 59).
  • the carbohydrates are enriched in the pulp after the fractionation reaction as is shown by the pulp composition.
  • the amount of lignin present in the pulp is lower (5.10 wt%) for the “both solvent and liquor recycle” reaction compared to the lignin content of 8.41 and 14.05 wt% for the “solvent recycle only” and “no recycle” reactions, respectively.
  • Figure 60 shows that monomer formation and stabilization step has occurred in the RCF step despite the presence of the aromatic and carbohydrate compounds (i.e., the crude lignin oil) in the reaction mixture.
  • Syringyl type monomers S-monomers
  • Figure 60A Syringyl type monomers
  • Figure 60B The GC-spectra of these refined lignin oils are shown in Figure 61.
  • the S-monomer formation is 12.3 wt% of the birch lignin for the case in which 75% of the liquor recycle stream is re-entered in the reactor and is 17.2 wt% of the birch lignin when none of the liquor recycle stream is re-entered in the reactor system (“solvent recycle only”).
  • the S-monomer yield is 14.3 wt% for pure ethanol RCF.
  • the typical GPC spectra in Figure 62 and the low number average ( ⁇ 500 g/mol) and weight average ( ⁇ 900 g/mol) molecular weights of the lignin oils in Table 12 show that the lignin has successfully depolymerized to monomers, dimers, and low molecular weight oligomers.
  • Figure 1 is a schematic view of one embodiment of the invention process 100 of converting lignocellulosic biomass into a pulp and a stream comprising aromatics and carbohydrates.
  • Figure 2 is a schematic view of one embodiment of the invention process 200A of converting lignocellulosic biomass into a pulp and a stream comprising aromatics and carbohydrates, further comprising steps to recover part of the alcohol that leaves the invention process 100 otherwise.
  • Figure 3 is a schematic view of one embodiment of the invention process 200B of converting lignocellulosic biomass into a pulp and a stream comprising aromatics and carbohydrates, further comprising the steps to produce an acetate ester.
  • Figure 4 is a schematic view of one embodiment of the invention process 200C of converting lignocellulosic biomass into a pulp and a stream comprising aromatics and carbohydrates, further comprising the steps produce acetic acid.
  • FIG. 5 is a schematic view showing the reactor mass balance of a reductive catalytic fractionation (RCF) reaction of birch, on a 100 kg wood wet basis.
  • RCF reductive catalytic fractionation
  • Figure 6 is a gel permeation chromatography (GPC) of the birch lignin oil obtained with a standard RCF reaction in methanol. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h.
  • GPC gel permeation chromatography
  • Figure 7 is a GC-chromatogram of the birch lignin oil obtained with a standard RCF reaction in methanol. The major monomer peaks are assigned on the chromatogram. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h.
  • Figure 8 is a GC-chromatogram of the aqueous phase obtained with a standard RCF reaction in methanol. The major peaks of the carbohydrate monomers and degradation products (ethylene glycol, glycerol) are assigned on the chromatogram. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h.
  • Figure 9 is a GC-chromatogram a) of methyl acetate solutions in methanol at concentrations between 0.01 and 0.08 M and b) the reaction liquor after RCF. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h. The methyl acetate peak is assigned on the spectrum.
  • Figure 10 depicts the chemical structure of the model compounds used to represent the crude lignin oil components in the Aspen HYSYS process simulation.
  • Figure 11 is a schematic overview of the combined heat and power plant (CHP) and its interaction with the process. The cooling water pump around is not shown, but consumes part of the electricity that is produced by the gas turbine. Typical efficiencies used in modelling this CHP are shown in Table 3.
  • Figure 12 is a process flow diagram of the process.
  • the process consists of three sections: (i) the reactor area and solvent recycle, where wood is converted, the reaction mixture is purified and solvents are recycled; (ii) the crude oil purification which produces a refined lignin oil an aqueous sugar solution by liquid-liquid extraction and (iii) the combined heat and power plant (CHP), which produces the power and heat that is consumed by the process by recuperating the chemical energy contained in off-gas and purge streams.
  • CHP combined heat and power plant
  • Figure 13 depicts the solvent composition when no solvent is recycled (i.e., No Recycle - 0 % of the streams entering split 1 and split 2 respectively are re-entered into the reactor), when only a part of the purified liquor is recycled (i.e., Liquor Recycle only - 75% of the stream entering split 1 is re-entered in the reactor, whereas 0% of the stream entering split 2 is re-entered in the reactor), when only a part (99.9 %) of the stream comprising methanol and methyl acetate (and some water) after distillation is recycled (i.e., Solvent Recycle Only), and when both streams are recycled with a ratio of 75% and 99.9% of the amount entering splits 1 and 2, respectively (i.e., Both Recycle).
  • Figure 14 depicts the solvent composition at the reactor inlet (left axis) and solvent volumetric flow rate at reaction conditions (right axis) in function of the distillation split ratio.
  • the distillation split ratio represents the percentual amount of the liquid enriched with crude lignin oil after reaction that is recycled back to the reactor section as parameterized in split 1 (see Figure 12).
  • the solvent volumetric flow rate at reaction conditions depends on the overall solvent composition at the reactor inlet. Fresh methanol is added to the recycled solvent streams to maintain a constant volumetric flow of 10 L per kg dry biomass at RT.
  • Figure 15 shows a) Operational expenditures (OPEX) in million € per year (M €.y -1 ) and b) capital expenditures (CAPEX) in million € (M €) of an RCF biorefinery processing 150 kt wood y 1 in function of the distillation split ratio.
  • OPEX Operational expenditures
  • CAEX capital expenditures
  • Figure 16 shows the minimum selling price of the refined lignin oil (MSP-RLO) in €.t -1 .
  • the selling price of benzene, phenol and bisphenol A were obtained from ICIS reports for the period 2019-2020. (8- 10)
  • the selling price of the lignin oil oligomers was set to 1750 €.t -1 to ensure an economic feasable operation of the biorefinery that also converts the lignin monomers to phenol for which a selling price of 1300 €.t -1 was used.
  • the minimum selling price of the lignin oil estimated by Bartling et al. amounts 1600 €.t -1 for their base design with methanol RCF.
  • FIG. 17 is a schematic view of the system boundary of the LCA.
  • the LCA covers the raw material extraction and processing to inputs of the RCF biorefmery as well as the emissions associated with producing the functional unit, i. e. , the refined lignin oil and the by-products viz. , the carbohydrate pulp and aqueous sugars.
  • Figure 18 is a schematic view showing the share of process in- and outputs to the total GWP of the refined lignin oil (GWP-RLO) and the total GWP compared to the benzene, phenol and bisphenol A GWP value, in function of the distillation split ratio.
  • the emissions were assigned to the refined lignin oil under economic allocation.
  • Figure 19 is a schematic view showing pulp composition relative to the composition of the birch wood feedstock fr a) RCF with pure methanol and with a solvent mixture comprising methanol, methyl acetate and water and with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil 75% for b) RCF reactions with solvent mixture comprising methanol, methyl acetate, water and crude lignin oil at various reaction temperature and reactor residence time.
  • RCF reactions conditions 4 g birch sawdust (pre-extracted, particle size 0.25 - 0.50 mm), 0.4 g of 5% Pd/C, 40 ml solvent (at RT), 220°C (unless mentioned otherwise), 30 bar H2 (at RT) and reaction time of 2 h (unless mentioned otherwise).
  • the base case with pure methanol as solvent is labeled as 220°C/2h - MeOH.
  • the first case, with a the solvent mixture comprising methanol, methyl acetate and water is labeled as 220°C/2h - MeOH + MA/H20. This solvent mixture consists of 65% MeOH, 30% MA and 5% H2O on a volumetric basis.
  • the second case with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil is labeled as 220°C/2h - MeOH + MA/H2O/CLO.
  • This solvent mixture consists of 43% MeOH, 37% MA, 12% H2O and 8% CLO on a volumetric basis.
  • the solvent volume was kept constant to 40 ml (at RT) for all reactions by assuming an CLO density of 0.9 g.cm-3, which was modelled by group contribution theory for mixtures of the CLO molecules with Aspen HYSYS ®. Reaction temperature and residence time were varied for the second case as indicated by the label.
  • the lignin content comprises the Klason and acid-soluble lignin as determined by the pulp analytical procedure.
  • Figure 20 is a schematic view showing the monomer yield of the syringyl-type monomeric units vs. pristine birch lignin content (left axis) and the degree of delignification (right axis) for a) RCF with pure methanol and with a solvent mixture comprising methanol, methyl acetate and water and with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil and for b) RCF reactions with solvent mixture comprising methanol, methyl acetate, water and crude lignin oil at various reaction temperature and reactor residence time. Similar labeling applies as in Figure 19.
  • Figure 21 is a schematic view showing the monomer composition of the refined lignin oil (left axis) and degree of delignification (right axis) for a) RCF with pure methanol and with a solvent mixture comprising methanol, methyl acetate and water and with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil and for b) RCF reactions with solvent mixture comprising methanol, methyl acetate, water and crude lignin oil at various reaction temperature and reactor residence time. Similar labeling applies as in Figure 19.
  • the monomer composition of the spruce lignin oil obtained from RCF with pure methanol is also shown and labeled as Spruce Lignin Oil.
  • the large quantity of G- monomeric units for the lignin oil obtained with a solvent composition mimicking a 75% split ratio originates from the spruce crude lignin oil, which was added to the solvent mixture before reaction.
  • Figure 22 shows the GC -chromatograms of the refined lignin oils for a standard RCF reaction using spruce (Spruce Lignin Oil) and, for RCF with pure methanol and with a solvent mixture comprising methanol, methyl acetate and water and with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil. Similar labeling applies as in Figure 19.
  • the major monomer peaks are assigned on the chromatogram. Peaks of the acetylated equivalents of the 4-n-propanol monomers are shifted to higher retention times.
  • Figure 23 is a schematic view showing the gel permeation chromatography profiles of the refined lignin oils for RCF with pure methanol and with a solvent mixture comprising methanol, methyl acetate and water and with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil and, for RCF reactions with solvent mixture comprising methanol, methyl acetate, water and crude lignin oil at various reaction temperature and reactor residence time. Similar labeling applies as in Figure 19.
  • the GPC profile of the spruce lignin oil obtained from RCF with pure methanol is also shown and labeled as Spruce.
  • Figure 24 shows the net heating, cooling and electric power requirements (in kW) of the process, presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 25 shows the hydrogen fuel intake (in kg/h) of the process, presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 26 shows the cooling water intake (in kg/h) of the process, presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 27 shows the pulp composition relative to the pristine birch composition (in %, left axis) and the delignification extent (in %, right axis) for the RCF reactions conducted with solvent mixtures, obtained in the process presented in Example 2 and shown in Figure 12, when none of the solvent and liquor recycle streams are re-entered in the reactor (“Pulp - No recycle”), when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Pulp - Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are reentered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“Pulp - both solvent and liquor recycle”).
  • the compositions for these solvent mixtures are given in Figure 13.
  • Figure 28 shows the net heating, cooling and electric power requirements (in kW) of the process, presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • Figure 29 shows the hydrogen fuel intake (in kg/h) of the process, presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • Figure 30 shows the cooling water intake (in kg/h) of the process, presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • Figure 31 shows the pulp composition relative to the pristine birch composition (in %, left axis) and the delignification extent (in %, right axis) for the RCF reactions conducted with solvent mixtures, obtained in the process presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Pulp - Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • Figure 14 The compositions for these solvent mixtures are given in Figure 14 at each corresponding distillation split ratio (%).
  • Figure 32 A) shows the monomer yield of the syringyl-type monomeric units vs. pristine birch lignin content (in %, left axis) and the degree of delignification (in %, right axis) and B) shows the monomer composition of the refined lignin oil (in %, left axis) and degree of delignification (in %, right axis) for the RCF reactions conducted with pure methanol (“MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is reentered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or
  • Figure 33 shows the GC-spectra of the refined lignin oils for the RCF reactions conducted with pure methanol (“Birch - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • the compositions for these solvent mixtures are given in Figure 14 at each corresponding distillation split ratio (%).
  • the GC-spectrum of the refined lignin oil obtained by RCF with a spruce lignocellulosic biomass and methanol is also shown as comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 14.
  • Figure 34 shows the GC-spectra of the aqueous phase for the RCF reactions conducted with pure methanol (“Birch - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • the compositions for these solvent mixtures are given in Figure 14 at each corresponding distillation split ratio (%).
  • the GC-spectrum of the aqueous phase obtained by RCF with a spruce lignocellulosic biomass and methanol is also shown as comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 14.
  • Figure 35 shows the GPC-spectra of the refined lignin oils for the RCF reactions conducted with pure methanol (“Birch - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% of the stream entering split 1 in the reactor (“liquor recycling”).
  • the compositions for these solvent mixtures are given in Figure 14 at each corresponding distillation split ratio (%).
  • the GPC-spectrum of the refined lignin oil obtained by RCF with a spruce lignocellulosic biomass and methanol is also shown as comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 14.
  • Figure 36 is a schematic view showing the reactor mass balance of an RCF reaction of spruce in methanol, on a 100 kg wood wet basis.
  • Figure 37 is a gel permeation chromatography (GPC) of the spruce lignin oil obtained with a standard RCF reaction in methanol. Reaction conditions: 4 g spruce sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h.
  • GPC gel permeation chromatography
  • Figure 38 is a GC-chromatogram of the spruce lignin oil obtained with a standard RCF reaction in methanol . The maj or monomer peaks are assigned on the chromatogram . Reaction conditions : 4 g spruce sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h.
  • Figure 39 is a GC-chromatogram of the aqueous phase obtained with a standard RCF reaction of spruce in methanol. The major peaks of the carbohydrate monomers and degradation products (ethylene glycol, glycerol) are assigned on the chromatogram. Reaction conditions: 4 g spruce sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h.
  • Figure 40 is a GC-chromatogram a) of methyl acetate solutions in methanol at concentrations between 0.01 and 0.08 M and b) the reaction liquor after RCF with spruce in methanol. Reaction conditions: 4 g spruce sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H2 (at RT), 220°C, 2 h. The methyl acetate peak is assigned on the spectrum.
  • Figure 41 depicts the solvent composition when no solvent is recycled (i.e., No Recycle - 0 % of the streams entering split 1 and split 2 respectively are re-entered into the reactor), when only a part of the purified liquor is recycled (z. e.
  • Liquor Recycle only - 80% of the stream entering split 1 is re-entered in the reactor, whereas 0% of the stream entering split 2 is re-entered in the reactor), when only a part (99.9 %) of the stream comprising methanol and methyl acetate (and some water) after distillation is recycled (i.e., Solvent Recycle Only), and when both streams are recycled with a ratio of 80% and 99.9% of the amount entering splits 1 and 2, respectively i.e., Both Solvent and Liquor Recycle), in the process presented in Example 2 and Figure 12 when spruce is used as the lignocellulosic biomass.
  • Figure 42 shows the net heating, cooling and electric power requirements (in kW) of the process, presented in Example 2 and shown in Figure 12 in which spruce is used as the lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 43 shows the hydrogen fuel intake (in kg/h) of the process, presented in Example 2 and shown in Figure 12 in which spruce is used as the lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 44 shows the cooling water intake (in kg/h) of the process, presented in Example 2 and shown in Figure 12 in which spruce is used as the lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 45 shows the pulp composition relative to the pristine spruce composition (in %, left axis) and the delignification extent (in %, right axis) for the RCF reactions conducted with spruce lignocellulosic biomass and solvent mixtures, obtained in the process presented in Example 2 and shown in Figure 12 in which spruce is used as lignocellulosic biomass, when none of the solvent and liquor recycle streams are re-entered in the reactor (“Pulp - No recycle”), when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Pulp - Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“Pulp - both solvent and liquor recycle”).
  • the compositions for these solvent mixtures are given in Figure 41.
  • Figure 46 shows the monomer composition of the refined lignin oil (in %, left axis) and degree of delignification (in %, right axis) for the RCF reactions conducted with spruce lignocellulosic biomass and pure methanol (“MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12 in which spruce is used as lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1 , respectively, in the reactor (“both solvent and liquor recycle”) .
  • the compositions for these solvent mixtures are given in Figure 41.
  • Figure 47 shows the GC-spectra of the refined lignin oils for the RCF reactions conducted with spruce lignocellulosic biomass and pure methanol (“Spruce - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12 in which spruce is used as lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“solvent and 80 % liquor recycling”).
  • the compositions for these solvent mixtures are given in Figure 41.
  • Figure 48 shows the GPC-spectra of the refined lignin oils for the RCF reactions conducted with spruce lignocellulosic biomass and pure methanol (“Spruce - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12 in which spruce is used as lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“solvent and 80 % liquor recycling”).
  • the compositions for these solvent mixtures are given in Figure 41.
  • Figure 49 is a schematic view showing the reactor mass balance of an RCF reaction of birch in ethanol, on a 100 kg wood wet basis.
  • Figure 50 is a gel permeation chromatography (GPC) of the birch lignin oil obtained with a standard RCF reaction in ethanol. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml ethanol, 30 bar H 2 (at RT), 220°C, 2 h.
  • GPC gel permeation chromatography
  • Figure 51 is a GC -chromatogram of the birch lignin oil obtained with a standard RCF reaction in ethanol. The major monomer peaks are assigned on the chromatogram. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml ethanol, 30 bar FF (at RT), 220°C, 2 h.
  • Figure 52 is a GC-chromatogram of the aqueous phase obtained with a standard RCF reaction of birch in ethanol. The major peaks of the carbohydrate monomers and degradation products (ethylene glycol, glycerol) are assigned on the chromatogram. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml ethanol, 30 bar H 2 (at RT), 220°C, 2 h.
  • Figure 53 is a GC-chromatogram a) of ethyl acetate solutions in ethanol at concentrations between 0.025 and 0.1 M and b) the reaction liquor after RCF with birch in ethanol. Reaction conditions: 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml ethanol, 30 bar H 2 (at RT), 220°C, 2 h. The ethyl acetate peak is assigned on the spectrum.
  • Figure 54 is a process flow diagram of the process.
  • the process consists of three sections: (i) the reactor area and solvent recycle, where wood is converted, the reaction mixture is purified and solvents are recycled; (ii) the crude oil purification which produces a refined lignin oil an aqueous sugar solution by liquid-liquid extraction and (iii) the combined heat and power plant (CHP), which produces the power and heat that is consumed by the process by recuperating the chemical energy contained in off-gas and purge streams.
  • CHP combined heat and power plant
  • Figure 55 depicts the solvent composition when no solvent is recycled (i.e., No Recycle - 0 % of the streams entering split 1 and split 2 respectively are re-entered into the reactor), when only a part of the purified liquor is recycled (i. e.
  • Liquor Recycle only - 75% of the stream entering split 1 is re-entered in the reactor, whereas 0% of the stream entering split 2 is re-entered in the reactor), when only a part (99.9 %) of the stream comprising ethanol and ethyl acetate (and some water) after distillation is recycled (i.e., Solvent Recycle Only), and when both streams are recycled with a ratio of 75% and 99.9% of the amount entering splits 1 and 2, respectively (i.e., Both Solvent and Liquor Recycle), in the process presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol.
  • Figure 56 shows the net heating, cooling and electric power requirements (in kW) of the process, presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by reentering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 57 shows the hydrogen fuel intake (in kg/h) of the process, presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 58 shows the cooling water intake (in kg/h) of the process, presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“both solvent and liquor recycle”).
  • Figure 59 shows the pulp composition relative to the pristine birch composition (in %, left axis) and the delignification extent (in %, right axis) for the RCF reactions conducted with solvent mixtures, obtained in the process presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when none of the solvent and liquor recycle streams are re-entered in the reactor (“Pulp - No recycle”), when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Pulp - Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“Pulp - both solvent and liquor recycle”).
  • FIG. 55 The compositions for these solvent mixtures are given in Figure 55.
  • Figure 60 A) shows the monomer yield of the syringyl-type monomeric units vs. pristine birch lignin content (in %, left axis) and the degree of delignification (in %, right axis) and B) shows the monomer composition of the refined lignin oil (in %, left axis) and degree of delignification (in %, right axis) for the RCF reactions conducted with pure ethanol (“EtOH”) and with solvent mixtures obtained in the process presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9%
  • Figure 61 shows the GC-spectra of the refined lignin oils for the RCF reactions conducted with birch lignocellulosic biomass and pure ethanol (“Birch - EtOH”) and with solvent mixtures obtained in the process presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“solvent and 75 % liquor recycling”).
  • the GC-spectrum of the refined lignin oil obtained by RCF with a spruce lignocellulosic biomass is also shown as comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 55.
  • Figure 62 shows the GPC-spectra of the refined lignin oils for the RCF reactions conducted with birch lignocellulosic biomass and pure ethanol (“Birch - EtOH”) and with solvent mixtures obtained in the process presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“solvent and 75 % liquor recycling”).
  • the GPC-spectrum of the refined lignin oil obtained by RCF with a spruce lignocellulosic biomass is also shown as comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 55. Supporting Tables
  • Table 1 contains the results of the Karl -Fischer titration of the solvent methanol, and the reaction mixture, after RCF reaction, from which the total water content of the birch and the water content present in the reaction mixture could be compared.
  • Reaction conditions 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H 2 (at RT), 220°C, 2 h.
  • Table 2 shows the composition of the gas phase after the RCF base reaction with pure methanol.
  • Reaction conditions 4 g birch sawdust (250 - 500 pm), 0.4 g Pd/C, 40 ml methanol, 30 bar H 2 (at RT), 220°C, 2 h.
  • Table 3 contains the parameters used in the CHP calculations: the efficiency of the boiler (%) and steam turbine (%) and the condensate return (%).
  • the condensate return equals the amount of high pressure, medium pressure and low-pressure condensate that is returned to the CHP boiler relative to the amount of high pressure, medium pressure and low pressure steam that has entered the process.
  • Table 4 shows the mass & energy balances of the RCF biorefinery at a distillation split ratio of 0%, 50% and 75%. A negative value for the energy streams corresponds to an excess production.
  • the ratio of the process energy input and the wood calorific value was approximated by division of the heating value of methanol and hydrogen input and the power input by the heating value the wood feedstock. Water is consumed in the liquid-liquid extraction, in the cooling water network and in the boilers for steam production.
  • T able 5 shows the economic parameters used in the techno-economic assessment of the RCF biorefmery process. Cost escalation indices and the location factor were obtained from Sinnott & Towler.
  • Table 5 gives a list of the process in- and output prices. Similar pricing was used as by Liao et al. (detailed info can be found in their supplementary info). Prices for the high, medium and low-pressure steam levels were obtained from Sinnott & Towler. Prices for bisphenol A, phenol and benzene were reported by ICIS, over a period between 2019-2020. Table 6
  • Table 7 contains the GWP values of the refinery in- and outputs. The background processes and technologies of the life cycle inventory (LCI) of each of these inputs are shown. The LCIs were obtained from Ecoinvent v3.8 and Thinkstep Gabi professional database. Table 7
  • Table 8 shows the number average molecular weight (M n ) and the weight average molecular weight (M w ) of the refined lignin oil for RCF with pure methanol and with a solvent mixture comprising methanol, methyl acetate and water and with a solvent mixture comprising methanol, methyl acetate, water and crude lignin oil and, for RCF reactions with solvent mixture comprising methanol, methyl acetate, water and crude lignin oil at various reaction temperature and reactor residence time. Similar labeling applies as in Figure 19.
  • the GPC profile of the spruce lignin oil obtained from RCF with pure methanol is also shown and labeled as Spruce. Table 8
  • Table 9 is showing the delignification (%), relative % change of the delignification and MSP and the GWP of the lignin oil in function of a distillation split ratio of 0% and 75% split and the reactor residence time and the reaction temperature at a 75% distillation split ratio.
  • the degree of delignification obtained with the experimental RCF was used to estimate increased lignin oil revenues compared to the methanol base case (62%) and relate the change in oil yield to the MSP and GWP obtained by TEA and LCA of the process simulation at various solvent composition.
  • Table 10 shows the number average molecular weight (M n ) and the weight average molecular weight (M w ) of the refined lignin oils for the RCF reactions conducted with pure methanol (“Birch - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“Solvent recycle only”) and when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% of the stream entering split 2 and 25%, 50%, 70%, 80% or 90% ofthe stream entering split 1 in the reactor (“X % recycling”).
  • compositions for these solvent mixtures are given in Figure 14 at each corresponding distillation split ratio (%).
  • the M n and M w of the refined lignin oil obtained by RCF with a spruce lignocellulosic biomass and methanol are also shown for comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 14.
  • Table 11 shows the number average molecular weight (M n ) and the weight average molecular weight (M w ) of the refined lignin oils for the RCF reactions conducted with spruce lignocellulosic biomass and pure methanol (“Spruce - MeOH”) and with solvent mixtures obtained in the process presented in Example 2 and shown in Figure 12 in which spruce is used as lignocellulosic biomass, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 80% of the streams entering splits 2 and 1, respectively, in the reactor (“solvent and 80 % liquor recycling”).
  • the compositions for these solvent mixtures are given in Figure 41.
  • Table 11 shows the number average molecular weight (M n ) and the weight average molecular weight (M w ) of the refined lignin oils for the RCF reactions conducted with birch lignocellulosic biomass and pure ethanol (“Birch - EtOH”) and with solvent mixtures obtained in the process presented in Example 21 and shown in Figure 54 in which birch is used as the lignocellulosic biomass and ethanol as the alcohol, when only the solvent recycle stream is re-entered in the reactor by re-entering 99.9% of the stream entering split 2 in the reactor (“solvent recycle only”) and of the same process when both the solvent recycle stream and the liquor recycle stream are re-entered in the reactor by re-entering 99.9% and 75% of the streams entering splits 2 and 1, respectively, in the reactor (“solvent and 75 % liquor recycling”).
  • the M n and M w of the refined lignin oil obtained by RCF with a spruce lignocellulosic biomass is also shown as comparison.
  • the spruce crude lignin oil was used to mimic the solvent mixtures shown in Figure 55.

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Abstract

La présente invention concerne un procédé de fractionnement de biomasse lignocellulosique en une pâte solide glucidique de haute qualité enrichie en cellulose et un flux comprenant des composés aromatiques, provenant de la fraction lignine de la biomasse lignocellulosique, et des composés glucidiques, provenant principalement de la fraction hémicellulose de la biomasse lignocellulosique, qui sont des précurseurs idéaux pour les produits chimiques, les carburants et les matériaux. L'invention concerne un procédé dans lequel l'étape de fractionnement est efficacement intégrée aux étapes de récupération et de recyclage des solvants, ce qui permet d'obtenir une composition unique et personnalisable du mélange de solvants dans l'étape de fractionnement qui améliore le fractionnement de la lignocellulose. De tels mélanges de solvants comprennent (i) un alcool, (ii) un ester d'acétate ayant une chaîne latérale identique à celle de l'alcool, (iii) de l'eau et (iv) les composés aromatiques et glucidiques obtenus par la mise en contact de la lignocellulose avec ledit mélange de solvants. L'ester d'acétate, l'eau et les composés aromatiques et glucidiques sont des (sous)-produits formés par réaction de l'alcool avec les groupes acétyles de la fraction hémicellulose de la biomasse lignocellulosique, libérés de la biomasse lignocellulosique dans le liquide de réaction et dissous à partir de la lignine et de la fraction glucidique (principalement l'hémicellulose) de la biomasse lignocellulosique, respectivement, au cours de l'étape de fractionnement.
PCT/EP2023/070028 2022-07-19 2023-07-19 Raffinerie de biomasse lignocellulosique WO2024017949A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0211558A2 (fr) * 1985-07-26 1987-02-25 Biodyne Chemicals, Inc. Procédé de digestion de matière lignocellulosique
US5730837A (en) * 1994-12-02 1998-03-24 Midwest Research Institute Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
WO2011133571A2 (fr) * 2010-04-19 2011-10-27 Board Of Trustees Of Michigan State University Biomasse lignocellulosique digestible, produits d'extraction du bois et procédés de production associés
WO2022090364A1 (fr) 2020-10-28 2022-05-05 Katholieke Universiteit Leuven Raffinerie de lignocellulose

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0211558A2 (fr) * 1985-07-26 1987-02-25 Biodyne Chemicals, Inc. Procédé de digestion de matière lignocellulosique
US5730837A (en) * 1994-12-02 1998-03-24 Midwest Research Institute Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
WO2011133571A2 (fr) * 2010-04-19 2011-10-27 Board Of Trustees Of Michigan State University Biomasse lignocellulosique digestible, produits d'extraction du bois et procédés de production associés
WO2022090364A1 (fr) 2020-10-28 2022-05-05 Katholieke Universiteit Leuven Raffinerie de lignocellulose

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Title
BARTLING ET AL., ENERGY & ENVIRONMENTAL SCIENCE, 2021, pages 4147 - 4168
LIAO ET AL., SCIENCE, 2020, pages 1385 - 1390

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