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WO2025109515A1 - Procédé de production de bio-huile à partir de lignine - Google Patents

Procédé de production de bio-huile à partir de lignine Download PDF

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Publication number
WO2025109515A1
WO2025109515A1 PCT/IB2024/061673 IB2024061673W WO2025109515A1 WO 2025109515 A1 WO2025109515 A1 WO 2025109515A1 IB 2024061673 W IB2024061673 W IB 2024061673W WO 2025109515 A1 WO2025109515 A1 WO 2025109515A1
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Prior art keywords
lignin
oil
bio
alcohol
comprised
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English (en)
Inventor
Cristina BONANOMI
Rino BONETTI
Silvia Pavoni
Davide Moscatelli
Edoardo TERRENI
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Eni SpA
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Eni SpA
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Publication of WO2025109515A1 publication Critical patent/WO2025109515A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/733—Compounds of undetermined constitution obtained from animals or plants
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B20/00—Preservation of edible oils or fats
    • A23B20/30—Preservation of other edible oils or fats, e.g. shortenings or cooking oils
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
    • A23D9/02—Other edible oils or fats, e.g. shortenings or cooking oils characterised by the production or working-up
    • A23D9/04—Working-up
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/34—Anti-oxidant compositions; Compositions inhibiting chemical change containing plant or animal materials of unknown composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/086—Hydrothermal carbonization
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C11B1/104—Production of fats or fatty oils from raw materials by extracting using super critical gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/081—Anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/544—Extraction for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the present invention relates to a process for producing bio-oil from lignin.
  • the present invention relates to a process for producing bio-oil from lignin, comprising the following steps: (a) subjecting the lignin to extraction of the oligomers in the presence of at least one alcohol operating at specified conditions of temperature and time; (b) subjecting the lignin essentially free of said oligomers obtained in step (a) to depolymerization in the presence of at least one alcohol operating in supercritical conditions, at specified conditions of temperature, pressure and time; (c) recovering the oily phase consisting of bio-oil from the mixture obtained in step (b).
  • the bio-oil obtained from the aforesaid process can be advantageously used, for example, as an antioxidant agent or anti-UV agent, in particular as an antioxidant agent or anti-UV agent in biofuels which can be used as such, or mixed with other fuels in diesel engines for automotive or aviation.
  • the biooil obtained from the aforesaid process can be advantageously used, for example, as an antioxidant agent in bio-feedstocks such as, for example, vegetable oils and animal or vegetable fats, in order to slow down their rancidity during transport and storage.
  • the present invention also relates to a bio-oil from lignin having the specific characteristics set out below.
  • the present invention also relates to the use of said bio-oil from lignin as an antioxidant agent or anti-UV agent, in particular as an antioxidant agent or anti-UV agent in biofuels which can be used as such, or mixed with other fuels in diesel engines for automotive or aviation.
  • the present invention also relates to the use of said bio-oil from lignin as an antioxidant agent in bio-feedstocks such as, for example, vegetable oils and animal or vegetable fats.
  • Lignin is one of the most industrially accumulated waste materials.
  • the main source of lignin waste (the second most common natural polymer on the planet, after cellulose) comes from the paper industry.
  • incinerators which are able to drastically reduce the volume thereof, while recovering energy.
  • this process involves the production of contaminants in both gaseous and solid form, with consequent emissions of carbon dioxide (CO2) and carbon monoxide (CO).
  • CO2 carbon dioxide
  • CO carbon monoxide
  • cellulose is extracted with the aim of obtaining glucose, which is then used in the fermentation process from which bio-alcohol, in particular bio-ethanol, is obtained, with the consequent high added value.
  • bio-alcohol in particular bio-ethanol
  • lignin remains a by-product and is disposed of, again, by incineration.
  • the extraction of lignin from lignocellulosic biomass which can be carried out by means of various technologies, for example, by chemical, physical, biological or mechanical means, is in fact necessary before subjecting said lignocellulosic biomass to the enzymatic hydrolysis process to obtain glucose, in order to avoid the inhibition of the enzymes usually used in said process.
  • US patent application US 2020/0231879 describes a process for producing a distilled fuel from lignin comprising: preparing a biomass-derived lignin solvent; dissolving the lignin in the solvent from biomass-derived lignin; and separating the undissolved lignin from the mineral matter to produce synthetic crude oil ("syncrude").
  • Step (ii) of the aforesaid process can be carried out at a temperature comprised between 325°C and 450°C, for a time comprised between 0 and 8 hours, at a solid/solvent weight/weight (w/w) ratio comprised between 0.02 and 0.43.
  • European patent EP 2435454 describes lignin derivatives recovered from a "pulping" treatment of lignocellulosic biomass wherein said lignin derivatives have an aliphatic hydroxyl content comprised between 1.5 mmol/g and 3.5 mmol/g, a Radical Scavenging Index (RSI) comprised between 35 and 60, and a weight-average molecular weight (M w ) comprised between 500 g/mol and 5000 g/mol.
  • RSI Radical Scavenging Index
  • M w weight-average molecular weight
  • the aforesaid lignin derivatives are said to be usable as antioxidant agents in thermoplastic and thermosetting polymers.
  • lignin polymers are said to be usable in various applications for the purpose of providing antioxidant, immunopotentiation, anti-mutagenic, antiviral and/or anti-bacterial activity and improving the general health of animals and humans.
  • a low bio-oil yield for example, less than 40% by weight with respect to the total weight of the lignin subjected to depolymerization
  • use of low solid (i.e., lignin)/solvent for example, less than 0.50 weight/weight (w/w) ratios
  • use of high depolymerization temperatures for example, greater than 300°C
  • obtaining high weight-average molecular weight (M w ) bio-oil for example, greater than 1000 Daltons
  • high gas production mainly carbon monoxide (CO) and carbon dioxide (CO2)
  • the Applicant has posed the problem of finding a process for producing biooil from lignin which is able to overcome the aforesaid drawbacks.
  • the Applicant has now found that the production of bio-oil from lignin can be advantageously carried out by means of a process comprising subjecting the lignin to an oligomer extraction step before subjecting it to a depolymerization step.
  • a process for producing bio-oil from lignin comprising the following steps: (a) subjecting the lignin to extraction of the oligomers in the presence of at least one alcohol, operating at specified temperature and time conditions; (b) subjecting the lignin essentially free of said oligomers obtained in step (a) to depolymerization in the presence of at least one alcohol operating in supercritical conditions at specified conditions of temperature, pressure and time; (c) recovering the oily phase consisting of bio-oil from the mixture obtained in step (b), capable of overcoming the aforesaid drawbacks.
  • the aforesaid process allows to: obtain high bio-oil yields (i.e., yields comprised between 40% and 60% by weight with respect to the total weight of the lignin subjected to depolymerization); conduct the depolymerization, operating at high solid (i.e., lignin)/alcohol weight (w/w) ratios (i.e., weight ratios greater than 0.40); conduct the depolymerization at temperatures not exceeding 300°C; obtain a lower gas yield (mainly consisting of a mixture of hydrocarbons having from 1 to 4 carbon atoms and, at a lesser percentage, other gases, for example, carbon monoxide(CO)) (gas yield less than or equal to 5% by weight with respect to the total weight of the lignin subjected to depolymerization); recycle the solvent, i.e., the alcohol used, at the extraction and/or depolymerization step, reducing solvent losses
  • bio-oil obtained from the aforesaid process can be advantageously used, for example, as an antioxidant agent or anti-UV agent, in particular as an antioxidant agent or anti-UV agent in biofuels which can be used as such, or mixed with other fuels in diesel engines for automotive or aviation.
  • bio-oil obtained from the aforesaid process can be advantageously used, for example, as an antioxidant agent in bio-feedstocks such as, for example, vegetable oils and animal or vegetable fats, in order to slow down their rancidity during transport and storage.
  • an aim of the present invention is a process for producing bio-oil from lignin, comprising the following steps:
  • step (a) subjecting the lignin to extraction of the oligomers in the presence of at least one alcohol having from 1 to 5 carbon atoms, preferably from 1 to 2 carbon atoms, operating at the boiling temperature of said alcohol or, in the case of a mixture of alcohols at the temperature of the higher-boiling alcohol, for a time comprised between 30 minutes and 90 minutes, preferably comprised between 40 minutes and 70 minutes, obtaining a liquid phase comprising oligomers and at least one alcohol and a solid phase comprising lignin essentially free of said oligomers; (b) subjecting the solid phase comprising lignin essentially free of said oligomers obtained in step (a) to depolymerization in the presence of at least one alcohol having from 1 to 5 carbon atoms, preferably from 1 to 2 carbon atoms, in supercritical conditions, operating at a temperature comprised between 200°C and 300°C, preferably comprised between 220°C and 295°C, at a pressure comprised between 40 bar and 1
  • step (c) recovering the oily phase consisting of bio-oil from the mixture (ii) obtained in step (b).
  • lignin essentially free of said oligomers means that if present, said oligomers are present in an amount less than or equal to 1% by weight, preferably less than or equal to 0.5% by weight, with respect to the total weight of the lignin.
  • lignin Any type of lignin, i.e., lignin deriving from the paper industry or from biorefineries, or from lignocellulosic materials of various kinds (e.g., grass clippings, pruning residuals, straw, grain processing waste, etc.) can be used for the purpose of the process object of the present invention.
  • lignin deriving from the paper industry or from biorefineries or from lignocellulosic materials of various kinds (e.g., grass clippings, pruning residuals, straw, grain processing waste, etc.) can be used for the purpose of the process object of the present invention.
  • said lignin in said step (a), can be selected, for example, from: pre-treated lignin from biorefineries, i.e., deriving from a process wherein the starting lignocellulosic biomass is subjected to a "steam explosion" process to separate the cellulosic matrix from the lignin, which is then subjected to a purification step, obtaining dried and purified lignin; non-pretreated lignin, from biorefinery, i.e.
  • said lignocellulosic biomass can be selected, for example, from:
  • guayule for example, maize (for example, maize stalks, maize cobs), soybean, cotton, flax, rapeseed, wheat (for example, wheat straw), rice (for example, rice straw, rice hulls, rice husk), sugar cane (for example, sugar cane straw, sugar cane bagasse), palm (for example, palm leaves, palm trunks, palm mibrids, palm empty fruit bunches);
  • algae such as, for example, microalgae or macroalgae, in particular macroalgae.
  • said lignin before being subjected to said step (a) of extraction, can be subjected to a preliminary grinding process.
  • said lignin can be ground up to obtaining particles having a diameter comprised between 0.05 mm and 0.5 mm, more preferably comprised between 0.08 mm and 0.15 mm. Particles having a diameter less than 0.15 mm are particularly preferred.
  • said at least one alcohol in said step (a) can be selected, for example, from methanol, ethanol, propanol, butanol, pentanol, or mixtures thereof; preferably from methanol, ethanol, or mixtures thereof.
  • said lignin and said at least one alcohol in said step (a) can be used in a weight/weight (w/w) ratio comprised between 0.05 and 1.1, preferably comprised between 0.1 and 1.
  • the solid phase comprising lignin essentially free of oligomers obtained in said step (a) can be subjected to washing with at least one alcohol having from 1 to 5 carbon atoms, preferably from 1 to 2 carbon atoms, even more preferably with the alcohol used in said step (a) of extraction, in an amount such as to maintain the weight/weight (w/w) ratio used in said step (a), and subsequently to filtration and drying.
  • the liquid phase comprising oligomers and at least one alcohol obtained in said step (a) can be subjected to evaporation, for example under vacuum or by means of rotation, obtaining alcohol and a solid residue comprising lignin.
  • the alcohol obtained can be recycled to the extraction step (a) and/or the following depolymerization step (b).
  • the solid residue comprising lignin can be dried and used as fuel, or sent as such to depolymerization step (b).
  • said solid residue comprising lignin is sent as such to depolymerization step (b).
  • said at least one alcohol in said step (b) can be selected, for example, from methanol, ethanol, propanol, butanol, pentanol, or mixtures thereof; preferably from methanol, ethanol, or mixtures thereof.
  • said at least one alcohol used in extraction step (a) and in depolymerization step (b) can be either of synthetic origin or of bio-origin (bioalcohol).
  • said lignin and said at least one alcohol can be used in a weight/weight (w/w) ratio comprised between 0.45 and 1.1, preferably comprised between 0.48 and 1.
  • the gas phase (i) obtained in step (b) of the aforesaid process is generally less than or equal to 5% by weight with respect to the weight (dry weight) of the starting lignin.
  • Said gas phase consists mainly of a mixture of hydrocarbons having from 1 to 4 carbon atoms or other gases [for example, carbon monoxide (CO)].
  • CO carbon monoxide
  • Such a gaseous phase after separation, a separation which can be carried out for example by depressurization of the pressure vessel in which said step (b) is carried out, before the mixture (ii) obtained in said step (b) is sent for separation, is generally sent for further treatments in order to enhance its combustible organic component.
  • step (c) of recovery of the oily phase consisting of bio-oil comprises the following steps: (ci) subject the mixture (ii) obtained in step (b) to separation, obtaining:
  • liquid phase comprising an oily phase consisting of bio-oil and at least one alcohol
  • step (c2) subjecting the solid phase (iii) obtained in step (cl) to purification and separation obtaining:
  • step (c3) combining the oily phase consisting of bio-oil (v) obtained in step (c2) to the liquid phase comprising an oily phase consisting of bio-oil and at least one alcohol (iv) obtained in step (cl) and subjecting the whole to evaporation obtaining:
  • said separation step (ci) can be carried out, for example, by means of filtration, decantation, centrifugation, preferably by means of filtration.
  • said purification step (ci) can be carried out, for example, by means of washing with at least one alcohol, preferably with at least one alcohol used in depolymerization step (b), more preferably methanol, ethanol, or mixtures thereof.
  • the separation in said step (C2) can be carried out, for example, by means of filtration, decantation, centrifugation, preferably by means of filtration.
  • the solid phase comprising carbon residues ("char") and optionally unconverted lignin (vi) can be dried, for example, in an oven, so as to remove the residual alcohol and fed to the depolymerization step (b); the oily phase consisting of bio-oil (v) is combined with the liquid phase (iv) obtained in the separation step (ci) and the whole is subjected to the evaporation step (C3), for example, under vacuum or by means of rotation.
  • the liquid phase comprising at least one alcohol (viii) can be purified in order to recover pure (i.e., regenerated) alcohol by means of distillation under vacuum, which can be fed to the extraction step (a) and/or to the depolymerization step (b), while the oily phase (vii) comprising bio-oil can be used as such.
  • the present invention also relates to bio-oil from lignin obtained by the aforesaid process.
  • a further aim of the present invention is a bio-oil from lignin having the following characteristics: weight-average molecular weight (M w ) less than or equal to 1100 Daltons, preferably comprised between 560 Daltons and 1000 Daltons; number average molecular weight (Mn) less than or equal to 400 Daltons, preferably comprised between 250 Daltons and 390 Daltons; percentage variation between the H/C ratio of the bio-oil from lignin and the H/C ratio of the starting lignin equal to at least 3% more, preferably comprised between 5% more and 50% more, compared to the H/C ratio of the starting lignin; percentage variation between the H/O ratio of the bio-oil from lignin and the H/O ratio of the starting lignin equal to at least 25% more, preferably comprised between 28% more and 120% more, compared to the H/C ratio of the starting lignin.
  • M w weight-average molecular weight
  • Mn number average molecular weight
  • the present invention relates to the use of bio-oil from lignin as an antioxidant agent or anti-UV agent.
  • bio-oil from lignin as an antioxidant agent or anti-UV agent, preferably as an antioxidant agent or anti-UV agent in bio-fuels which can be used as such, or in mixtures with other fuels in diesel engines for automotive or aviation.
  • bio-oil from lignin as an antioxidant agent in bio-feedstocks such as vegetable oils and animal or vegetable fats.
  • FIG. 1 schematically illustrates an embodiment of the process object of the present invention.
  • lignin (1) for example, lignin from a biorefinery
  • an oligomers extraction step (2) in the presence of at least one alcohol (for example, methanol, ethanol), obtaining a liquid phase (3) comprising oligomers and at least one alcohol, and a solid phase (4) comprising lignin essentially free of oligomers.
  • at least one alcohol for example, methanol, ethanol
  • Said solid phase (4) after optional washing with alcohol (for example, methanol, ethanol), filtration and drying, is subjected to a depolymerization step (5) in the presence of at least one alcohol (for example, methanol, ethanol), obtaining a gas phase (6) and a mixture (7) comprising an oily phase consisting of bio-oil, a liquid phase comprising at least one alcohol and a solid phase comprising carbon residues ("char"), an oily phase consisting of bio-oil and, optionally, unconverted lignin.
  • alcohol for example, methanol, ethanol
  • Said mixture (7) is sent to separation (8) (for example, by filtration), obtaining a solid phase (10) comprising carbon residues ("char"), an oily phase consisting of bio-oil and, optionally, unconverted lignin, and a liquid phase (9) comprising an oily phase consisting of bio-oil and at least one alcohol.
  • separation (8) for example, by filtration
  • the solid phase (10) is subjected to purification and separation (11), obtaining an oily phase (13) consisting of bio-oil which is combined with the liquid phase (9) comprising an oily phase consisting of bio-oil and at least one alcohol and a solid phase (12) comprising carbon residue ("char") and optionally unconverted lignin which can be dried in order to remove the alcohol completely and subsequently recycled to the depolymerization step (not shown in Figure 1).
  • the liquid phase (9) to which the oily phase (13) consisting of bio-oil has also been added is sent to evaporation (14), obtaining a liquid phase (15) comprising at least one alcohol which is recycled to the extraction step (2) and/or to the depolymerization step (5) and an oily phase (16) comprising bio-oil.
  • the bio-oil obtained in the following examples was subjected to molecular weight determination by Gel Permeation Chromatography (GPC) on an Agilent 1100 GPC using two PFG M (PSS) columns connected in series with an Agilent 1100 VWD/UV detector operating at wavelengths comprised between 200 nm and 300 nm, connected in turn to an RI detector with hexafluoro-2-propanol (HFIP) eluent.
  • the samples of bio-oil from lignin obtained in the examples provided below were diluted in hexafluoro-2-propanol (HFIP) at a concentration of approximately 5 mg/mL.
  • the samples were then filtered on 0.2 nm polytetrafluroethylene (PTFE) filters before being inserted for analysis. The analysis was carried out at a flow rate of 1 mL/min, at 40°C, for approximately 40 minutes.
  • the weight-average molecular weight (M w ), number-average molecular weight (M n ) and poly dispersity index (i.e., the M w /M n ratio) were assessed by means of polyethylene terephthalate (PET) standards. Determination of H/C and H/O ratios
  • the elemental analysis CHNS(O) was performed using an ICP-OES analyser (ICAP 6500 DV Thermo Fisher Scientific, Waltham, MA, USA). This analysis allows the amounts of carbon (C), hydrogen (H), nitrogen (N), sulphur (S) and oxygen (O) present in a sample to be determined.
  • the sample to be analysed (2 mg) was placed in a tin crucible which was then closed to ensure that the sample was well sealed inside.
  • the crucible was then placed in the aforesaid elemental analyser and, using the software connected to it, the percentages of C, H, N and S were obtained. From these values, the H/C and H/O ratios were obtained.
  • the liquid phase was subjected to evaporation by means of Rotavapor operating at 650 mbar and 85°C, for 30 minutes, in order to recover the methanol (387.1 g) which can be recycled to the oligomer extraction step and/or to the depolymerization step and the oligomers (4.52 g).
  • the solid residue comprising lignin can be sent as such to depolymerization.
  • the solid phase (60 g) was fed to a 500 ml reactor to which 120 g of methanol was added [lignin/methanol (w/w) ratio equal to 0.5]: the whole was kept, under stirring, at 250°C, at 130 bar, for 120 minutes, obtaining a gas phase (about 3.5 g) which was removed by depressurization and a mixture comprising an oily phase consisting of bio-oil, a liquid phase comprising methanol and a solid phase comprising carbon residues ("char”), an oily phase consisting of bio-oil and unconverted lignin.
  • the aforesaid mixture was subjected to separation by means of filtration, obtaining a solid phase comprising carbon residues ("char"), an oily phase consisting of bio-oil and unconverted lignin (40 g), and a liquid phase comprising an oily phase consisting of bio-oil and methanol (136.5 g).
  • the aforesaid solid phase was subjected to purification and separation.
  • said solid phase was placed in a 250 ml beaker, equipped with a magnetic stirrer, and 100 g of pure methanol was added: the whole was kept, under stirring, at room temperature (25°C), for 15 minutes.
  • the resulting mixture was subjected to separation by means of filtration twice, obtaining an oily phase consisting of bio-oil (105 g), which was then combined with the aforesaid liquid phase comprising an oily phase consisting of bio-oil and methanol, and a solid phase comprising carbon residues ("char") and unconverted lignin, which was dried in an oven, at 85°C and 10 mbar, for 10 hours so as to completely remove the residual methanol: the amount of final dried solid corresponds to approximately 30 g.
  • the oily phase consisting of bio-oil was subjected to molecular weight and H/C and H/O ratio determination, operating as described above.
  • the liquid phase was subjected to evaporation by means of Rotavapor operating at 650 mbar and 85°C, for 30 minutes, in order to recover the ethanol (516.2 g) which can be recycled to the oligomer extraction step and/or to the depolymerization step and the oligomers (4.5 g).
  • the solid residue comprising lignin can be sent as such for depolymerization.
  • the solid phase (60 g) was fed to a 500 ml reactor to which 120 g of ethanol was added [lignin/ethanol (w/w) ratio equal to 0.5]: the whole was kept, under stirring, at 250°C, at 130 bar, for 120 minutes, obtaining a gas phase (about 3.4 g) which was removed by depressurization and a mixture comprising an oily phase consisting of bio-oil, a liquid phase comprising ethanol and a solid phase comprising carbon residues ("char”), an oily phase consisting of bio-oil and unconverted lignin.
  • the aforesaid mixture was subjected to separation by means of filtration, obtaining a solid phase comprising carbon residues ("char"), an oily phase consisting of bio-oil and unconverted lignin (40 g), and a liquid phase comprising an oily phase consisting of bio-oil and ethanol (136.6 g).
  • aforesaid solid phase was subjected to purification and separation.
  • said solid phase was placed in a 250 ml beaker, equipped with a magnetic stirrer, and 100 ml of pure ethanol was added: the whole was kept, under stirring, at room temperature (25°C), for 15 minutes.
  • the resulting mixture was subjected to separation by means of filtration twice, obtaining an oily phase consisting of bio-oil (102.6 g), which was then combined with the aforesaid liquid phase comprising an oily phase consisting of bio-oil and ethanol, and a solid phase comprising carbon residues ("char") and unconverted lignin, which was dried in an oven, at 85°C and 10 mbar, for 10 hours so as to completely remove the residual ethanol: the amount of final dried solid corresponds to approximately 32.4 g.
  • the oily phase consisting of bio-oil was subjected to molecular weight and H/C and H/O ratio determination, operating as described above.
  • the bio-oil obtained in Example 2 was compared with a commercial antioxidant [butylated hydroxytoluene (BHT - Merck)] using the Rancimat Test in accordance with standard EN 15751-2014: said test allowed to determine the oxidation stability of the bio-oil by measuring the induction period up to a maximum of 48 hours.
  • BHT - Merck butylated hydroxytoluene
  • a sample was prepared by mixing commercial, antioxidant- free, food-grade sunflower oil with the bio-oil obtained in Example 2 so as to have a bio-oil concentration equal to 1% by weight with respect to the total weight of the sunflower oil (Sample A).
  • the sample thus prepared was inserted into the Rancimat apparatus (Metrohm Herisau Switzerland).
  • samples were prepared by mixing commercial, antioxidant-free, food-grade sunflower oil with: commercial antioxidant butylated hydroxytoluene (BHT - Merck) so that the concentration of butylated hydroxytoluene (BHT) is equal to 0.3% by weight with respect to the total weight of the sunflower oil (Sample B); pre-treated lignin from biorefineries as used in Example 2 as such so as to have a concentration of lignin as such equal to 1% by weight with respect to the total weight of the sunflower oil (Sample C); oligomers obtained as shown in Example 2 so as to have a concentration of oligomers equal to 1% by weight with respect to the total weight of the sunflower oil (Sample D).
  • BHT - Merck commercial antioxidant butylated hydroxytoluene
  • Sample E consisting of commercial, antioxidant- free, food-grade sunflower oil as such, is also shown in Figure E
  • Sample E consisting of commercial, antioxidant-free, food-grade sunflower oil as such, is also shown in Figure 3.
  • a (previously calibrated) oxygen-sensitive probe was inserted: the whole was kept under magnetic stirring, the temperature was brought to 130°C, and the consumption of oxygen due to the auto-oxidation of the sunflower oil was then measured by means of said oxygen-sensitive probe.

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Abstract

L'invention concerne un procédé de production de bio-huile à partir de lignine comprenant les étapes suivantes : (a) la soumission de la lignine à une extraction des oligomères en présence d'au moins un alcool ayant de 1 à 5 atomes de carbone, de préférence de 1 à 2 atomes de carbone, opérant à la température d'ébullition dudit alcool ou, dans le cas d'un mélange d'alcools à la température de l'alcool comprenant le point d'ébullition le plus élevé, pendant une durée comprise entre 30 minutes et 90 minutes, de préférence comprise entre 40 minutes et 70 minutes, l'obtention d'une phase liquide comprenant des oligomères et au moins un alcool et une phase solide comprenant de la lignine essentiellement exempte desdits oligomères ; (b) la soumission de la phase solide comprenant de la lignine essentiellement exempte desdits oligomères obtenus à l'étape (a) à une dépolymérisation en présence d'au moins un alcool ayant de 1 à 5 atomes de carbone, de préférence de 1 à 2 atomes de carbone, dans des conditions supercritiques, opérant à une température comprise entre 200 °C et 300 °C, de préférence comprise entre 220 °C et 295 °C, à une pression comprise entre 40 bars et 170 bars, de préférence comprise entre 50 bars et 150 bars, pendant une durée comprise entre 5 minutes et 150 minutes, de préférence comprise entre 10 minutes et 130 minutes, obtenant : - (i) une phase gazeuse ;- (ii) un mélange comprenant une phase huileuse constituée de bio-huile, une phase liquide comprenant au moins un alcool et une phase solide comprenant des résidus carbonés ("produit de carbonisation"), une phase huileuse constituée de bio-huile et éventuellement de lignine non convertie ; (c) la récupération de la phase huileuse constituée de bio-huile à partir du mélange (ii) obtenu à l'étape (b). La bio-huile obtenue à partir du procédé susmentionné peut être avantageusement utilisée, par exemple, en tant qu'agent antioxydant ou agent anti-UV, en particulier en tant qu'agent antioxydant ou agent anti-UV dans des biocarburants qui peuvent être utilisés en tant que tels, ou mélangés avec d'autres carburants dans des moteurs diesel pour automobile ou aviation. En outre, la bio-huile obtenue à partir du procédé précité peut être avantageusement utilisée, par exemple, comme agent antioxydant dans des bio-charges telles que des huiles végétales et des graisses animales ou végétales, afin de ralentir leur rancidité pendant le transport et le stockage.
PCT/IB2024/061673 2023-11-24 2024-11-21 Procédé de production de bio-huile à partir de lignine Pending WO2025109515A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009028969A1 (fr) 2007-08-31 2009-03-05 Biojoule Ltd Lignine et autres produits isolés de matières végétales, procédés et compositions associés
WO2010037178A1 (fr) 2008-10-01 2010-04-08 Licella Pty Ltd Procédé de production d'huile biologique
EP2435454A1 (fr) 2009-05-28 2012-04-04 Lignol Innovations Ltd. Dérivés de lignine naturelle provenant de charges d'alimentation fibreuses annuelles
WO2016113280A1 (fr) 2015-01-13 2016-07-21 Danish Technical University Huiles de lignine solubles dans du gazole et leurs procédés de production
US20170240934A1 (en) * 2016-02-19 2017-08-24 Iowa State University Research Foundation, Inc. Pyrolysis of lignin
WO2019053287A1 (fr) 2017-09-18 2019-03-21 Technische Universiteit Eindhoven Procédé d'obtention d'une composition stable de lignine : solvant organique polaire par l'intermédiaire de modifications solvolytiques légères
US20200231879A1 (en) 2017-07-14 2020-07-23 Battelle Memorial Institute Lignin to liquid fuels and polyols using biomass-derived solvents
US20200399549A1 (en) * 2018-02-16 2020-12-24 A.P. Møller - Mærsk A/S A biofuel composition comprising lignin
WO2022125709A1 (fr) * 2020-12-09 2022-06-16 Virdia, Llc Procédés d'extraction de lignine

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009028969A1 (fr) 2007-08-31 2009-03-05 Biojoule Ltd Lignine et autres produits isolés de matières végétales, procédés et compositions associés
WO2010037178A1 (fr) 2008-10-01 2010-04-08 Licella Pty Ltd Procédé de production d'huile biologique
US20110209387A1 (en) * 2008-10-01 2011-09-01 Licella Pty Ltd Bio-Oil Production Method
EP2435454A1 (fr) 2009-05-28 2012-04-04 Lignol Innovations Ltd. Dérivés de lignine naturelle provenant de charges d'alimentation fibreuses annuelles
WO2016113280A1 (fr) 2015-01-13 2016-07-21 Danish Technical University Huiles de lignine solubles dans du gazole et leurs procédés de production
US20170240934A1 (en) * 2016-02-19 2017-08-24 Iowa State University Research Foundation, Inc. Pyrolysis of lignin
US20200231879A1 (en) 2017-07-14 2020-07-23 Battelle Memorial Institute Lignin to liquid fuels and polyols using biomass-derived solvents
WO2019053287A1 (fr) 2017-09-18 2019-03-21 Technische Universiteit Eindhoven Procédé d'obtention d'une composition stable de lignine : solvant organique polaire par l'intermédiaire de modifications solvolytiques légères
US20200399549A1 (en) * 2018-02-16 2020-12-24 A.P. Møller - Mærsk A/S A biofuel composition comprising lignin
WO2022125709A1 (fr) * 2020-12-09 2022-06-16 Virdia, Llc Procédés d'extraction de lignine

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LIAO JING JING ET AL: "Current advancement on the isolation, characterization and application of lignin", INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, ELSEVIER BV, NL, vol. 162, 24 June 2020 (2020-06-24), pages 985 - 1024, XP086280620, ISSN: 0141-8130, [retrieved on 20200624], DOI: 10.1016/J.IJBIOMAC.2020.06.168 *
LIXIONG LI ET AL: "Interaction of supercritical fluids with lignocellulosic materials", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, AMERICAN CHEMICAL SOCIETY, vol. 27, 1 January 1988 (1988-01-01), pages 1301 - 1312, XP002565486, ISSN: 0888-5885, DOI: 10.1021/IE00079A035 *
UMAR Y. ET AL., RENEWABLE ENERGY, vol. 182, 2022, pages 867 - 878

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