WO2015199608A1 - Dépolymérisation de lignine - Google Patents

Dépolymérisation de lignine Download PDF

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Publication number
WO2015199608A1
WO2015199608A1 PCT/SE2015/050745 SE2015050745W WO2015199608A1 WO 2015199608 A1 WO2015199608 A1 WO 2015199608A1 SE 2015050745 W SE2015050745 W SE 2015050745W WO 2015199608 A1 WO2015199608 A1 WO 2015199608A1
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WIPO (PCT)
Prior art keywords
lignin
weight
solvent
mixture
depolymerized
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PCT/SE2015/050745
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English (en)
Inventor
Alexander PAPTCHIKINE
Christian DAHLSTRAND
Joakim LÖFSTEDT
Joseph Samec
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Ren Fuel K2B Ab
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Publication of WO2015199608A1 publication Critical patent/WO2015199608A1/fr

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    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

Definitions

  • the present invention relates to a method of depolymerizing lignin using a sulfur containing agent in order to increase the solubility of lignin in carrier liquids.
  • the invention further relates to a composition comprising said depolymerized lignin.
  • Biomass includes, but is not limited to, plant parts, fruits, vegetables, processing waste, wood chips, chaff, grain, grasses, com, com husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and paper products, lignocellulosic material, lignin and any cellulose containing biological material or material of biological origin.
  • An important component of biomass is the lignin present in the solid portions of the biomass. Lignin comprises chains of aromatic and oxygenate constituents forming larger molecules that are not easily treated. A major reason for difficulty in treating the lignin is the inability to disperse the lignin for contact with catalysts that can break the lignin down.
  • Lignin is one of the most abundant natural polymers on earth.
  • One common way of preparing lignin is by separation from wood during pulping processes. Only a small amount (1-2 %) is utilized in specialty products whereas the rest primary serves as fuel. Even if burning lignin is a valuable way to reduce usage of fossil fuel, lignin has significant potential as raw material for the sustainable production of chemicals and fuel.
  • lignin differ structurally depending on the raw material source and subsequent processing, but one common feature is a backbone consisting of various substituted phenyl propane units that are bound to each other via aryl ether or carbon-carbon linkages. They are typically substituted with methoxy groups and the phenolic and aliphatic hydroxyl groups provide sites for e.g. further functionalization. Lignin is known to have a low ability to sorb water compared to for example the hydrophilic cellulose.
  • lignin may be used as a component in for example pellet fuel as a binder but it may also be used as an energy source due to its high energy content.
  • Lignin has higher energy content than cellulose or hernicelluloses and one gram of lignin has on average 2.27 J, which is 30% more than the energy content of cellu!osic carbohydrate.
  • the energy content of lignin is similar to that of coal.
  • Today due to its fuel value lignin that has been removed using the kraft process, sulphate process, in a pulp or paper mill, is usually burned in order to provide energy to run the production process and to recover the chemicals from the cooking liquor.
  • Lignoboost® is a separation process developed by Innventia AB and the process has been shown to increase the lignin yield using less sulphuric acid.
  • Lignoboost® process black liquor from the production processes is taken and the lignin is precipitated through the addition and reaction with acid, usually carbon dioxide (CO2) , and the lignin is then filtered off.
  • acid usually carbon dioxide (CO2)
  • CO2 carbon dioxide
  • the lignin filter cake is then re- dispersed and acidified, usually using sulphuric acid, and the obtained slurry is then filtered and washed using displacement washing.
  • the lignin is usually then dried and pulverized in order to make it suitable for lime kiln burners or before pelletizing it into pellet fuel.
  • Biofuel such as biogasoline and biodiesel
  • biomass material or gases such as wood, corn, sugarcane, animal fat, vegetable oils and so on.
  • biofuel industries are struggling with issues like food vs fuel debate, efficiency and the general supply of raw material.
  • pulp or paper making industries produces huge amounts of lignin which is often, as described above, only burned in the mill.
  • Two common strategies for exploring biomass as a fuel or fuel component are to use pyrolysis oils or hydrogenated lignin.
  • lignin In order to make lignin more useful one has to solve the problem with the low solubility of lignin in organic solvents.
  • One drawback of using lignin as a source for fuel production is the issue of providing lignin or lignin derivatives in a form suitable for hydrotreaters or crackers. The problem is that lignin is not soluble in oils or fatty acids which is, if not necessary, highly wanted.
  • Prior art provides various strategies for degrading lignin into small units or molecules in order to prepare lignin derivatives that may be processed. These strategies include hydrogenation, dexoygenation and acid catalyst hydrolysis.
  • WO2011003029 relates to a method for catalytic cleavage of carbon-carbon bonds and carbon-oxygen bonds in lignin.
  • US20130025191 relates to a depolymerisation and deoxygenation method where lignin is treated with hydrogen together with a catalyst in an aromatic containing solvent.
  • Many of the prior art methods for depolymerizing lignin involves multiple steps, high temperatures and pressure and consume a lot of reagents.
  • the economic benefits of producing fuels from biomass depend for example on an efficient process for preparing the lignin and on the preparation of the lignin or lignin derivatives so that the fuel production is as efficient as possible.
  • the amount oxygen should be as low as possible and the number of preparation steps should be as few as possible.
  • the object of the present invention is present a novel method of depolymerizing lignin in a straight forward way which does not require high temperatures or high pressure.
  • the depolymerized lignin may be used to prepare compositions which could be used to prepare a wide variety of products such as biofuels, chemicals, or additives.
  • By depolymerizing lignin the solubility of the lignin in various solvents increases.
  • the present invention relates to a method of depolymerizing lignin comprising: a. Providing a lignin containing aqueous solution in a container;
  • the present relates to depolymerized lignin obtained by the method according to the present invention.
  • the present invention relates to a composition
  • a composition comprising the depolymerized lignin according to the present invention and a carrier liquid and optionally an organic solvent.
  • the present invention relates to a composition comprising the depolymerized lignin according to the present invention and an organic solvent.
  • the present invention relates to the use of the depolymerized lignin or the composition according to the present invention for preparing fuel.
  • the preset invention relates to a fuel obtained by hydrotreating or hydro cracking the depolymerized lignin or a composition according to the present invention.
  • FIG 7 GPC of starting material and depolymerized lignin from examples 20-22.
  • Figure 8 GPC of starting material and depolymerized lignin from examples 23-25.
  • lignin means a polymer comprising coumaryl alcohol, coniferyl alcohol and sinapyl alcohol monomers.
  • lignin derivative means molecules or polymers derived from lignin.
  • lignin derivative and “molecules or polymers derived from lignin” are used interchangeably. These molecules or polymers may be a result of chemical modification or degradation of lignin or a lignin source, for example when treating black or red liquor in order to precipitate or separate lignin.
  • the lignin derivative has weight average molecular weight of not more than 1,000 g/mol, preferably not more than 800 g/mol. In one embodiment the lignin derivative has weight average molecular weight of 400-900g/mol.
  • the "repeating unit of lignin" is assumed to be 180 g/mol.
  • carrier liquid means a liquid selected from fatty acids or mixture of fatty acids, esterified fatty acids, rosin acid, crude oil, mineral oil, bunker fuel and hydrocarbon oils or mixtures thereof.
  • the substance For a substance to be processed in a refinery such as an oil refinery or bio oil refinery, the substance needs to be in liquid phase. Either the substance is in liquid phase at a given temperature (usually below 80 °C) or the substance is solvated in a liquid. In this patent application, such liquid will be given the term carrier liquid.
  • the present invention presents a composition and a method of preparing said composition where the composition comprises a biomass material, preferably lignin or lignin derivatives, where the biomass material is in liquid phase and may be processed in a refinery.
  • Biomass includes, but is not limited to wood, fruits, vegetables, processing waste, chaff, grain, grasses, com, com husks, weeds, aquatic plants, hay, paper, paper products, recycled paper, shell, brown coal, algae, straw, bark or nut shells, lignocellulosic material, lignin and any cellulose containing biological material or material of biological origin.
  • the biomass is wood, preferably particulate wood such as saw dust or wood chips.
  • the wood may be any kind of wood, hard or soft wood, coniferous tree or broad-leaf tree.
  • a non-limiting list of woods would be pine, birch, spruce, maple, ash, mountain ash, redwood, alder, elm, oak, larch, yew, chestnut, olive, cypress, banyan, sycamore, cherry, apple, pear, hawthorn, magnolia, sequoia, walnut, karri, coolabah and beech. It is preferred that the biomass contains as much lignin as possible.
  • the Kappa number estimates the amount of chemicals required during bleaching of wood pulp in order to obtain a pulp with a given degree of whiteness. Since the amount of bleach needed is related to the lignin content of the pulp, the Kappa number can be used to monitor the effectiveness of the lignin- extraction phase of the pulping process. It is approximately proportional to the residual lignin content of the pulp.
  • K Kappa number
  • c constant ⁇ 6.57 (dependent on process and wood)
  • 1 lignin content in percent.
  • the Kappa number is determined by ISO 302 :2004.
  • the Kappa number is determined by ISO 302 :2004.
  • the kappa number may be 20 or higher, or 40 or higher, or 60 or higher. In one embodiment the kappa number is 10- 100.
  • Biomass materials and derivatives thereof often have a general formula of C x HyO z where the ratio z /x depends of origin, part of the plant and also processes of the biomass material, and where x and. y each are > 1 and z>0.
  • x is >2 , or more preferably x is >3 , or more preferably x is >6; z is preferably > 1 , or >2.
  • x is ⁇ 20
  • x in another embodiment x is ⁇ 15, and in yet another embodiment x is ⁇ 1 1.
  • z is ⁇ 10 and in another embodiment z is ⁇ 5.
  • the biomass material may comprise other heteroatoms such as S or N.
  • biomass materials cellulose
  • palmitoleic oil C16H32O2
  • oleic acid C18H34O2
  • tall oil or fatty acid C17H31-35COOH rosin acids such as abeitic acid (C20H30O2)
  • lignin or lignin derivatives in the range between of C I to C20 such as (C10H10O2) , (C10H12O3) , (C11H14O4) , lignin in black liquor such as (CioHeO), (C10H10O2) , (C11H12O3) and pyrolysis oil, etc.
  • fatty acids such as palmitoleic oil (C16H32O2) , oleic acid (C18H34O2) , tall oil or fatty acid C17H31- 35COOH; rosin acids such as abeitic acid (C20H30O2) ; may also be used as a component in the composition according to the present invention.
  • fatty acids such as palmitoleic oil (C16H32O2) , oleic acid (C18H34O2) , tall oil or fatty acid C17H31- 35COOH; rosin acids such as abeitic acid (C20H30O2) ; may also be used as a component in the composition according to the present invention.
  • the biomass material is lignin or lignin derivatives in the range between of CI to C20, such as (C9H10O2) , (C10H12O3) and (C11H14O4) or lignin in or from black liquor such as (CgHeO), (C10H10O2) and (C11H12O3) .
  • lignin derivatives are guaiacol, coniferyl alcohol, sinapyl alcohol, ethyl 4-hydroxy-3- methoxy ketone, (4-hydroxy-3-methoxy-phenyl)-propen, vanillin and phenol.
  • the biomass material may be a mixture of biomass materials and in one
  • the biomass material is black or red liquor, or materials obtained from black or red liquor.
  • Black and red liquor contains cellulose, hemi cellulose and lignin and derivatives thereof.
  • the composition according to the present invention may comprise black or red liquor, or lignin or lignin derivatives obtained from black or red liquor.
  • the biomass material comprises residual material from ethanol production such as cellulosic or corn ethanol production, hereafter called ethanol production.
  • the biomass material is lignin or lignin derivatives obtained from ethanol production.
  • the biomass material comprises hydroxyl groups.
  • Black liquor comprises four main groups of organic substances, around 30-45 weight% biomass material, 25-35 weight% saccharine acids, about 10 weight% formic and acetic acid, 3-5 weight% extractives, about 1 weight% methanol, and many inorganic elements and sulfur.
  • the exact composition of the liquor varies and depends on the cooking conditions in the production process and the feedstock.
  • Red liquor comprises the ions from the sulfite process (calcium, sodium,
  • the lignin may be Kraft lignin, sulfonated lignin, Lignoboost® lignin, precipitated lignin, filtrated lignin, acetosolv lignin or organosolv lignin.
  • the lignin is Kraft lignin, acetosolv lignin or organosolv lignin.
  • the lignin is Kraft lignin.
  • the lignin is organosolv lignin.
  • the lignin may be in particulate form with a particle size of 5 mm or less, or 1 mm or less.
  • Lignin is not soluble in most organic solvents, fatty acids or oils. Instead prior art have presented various techniques to depolymerize and covert the depolymerized lignin into components soluble in the wanted media.
  • the present invention provides a method for increasing the solubility of lignin in organic solvents and carrier liquids by depolymerizing the lignin.
  • the weight average molecular weight (M w ) of the lignin in the lignin containing solution is 2000-5000g/mol Depolymerization of lignin
  • Lignin may be depolymerized according to the present invention by providing a lignin containing aqueous solution and mixing it with a sulfur containing reducing agent.
  • the pH of the formed mixture may be adjusted to a pH of 5.0 or higher for example 6.0 or higher, or 6.5 or higher, or 7.0 or higher, or 8.0 or higher, or 9.0 or higher, but preferably 14.0 or lower, or 12 or lower, or 1 1.5 or lower, or 11.0 or lower.
  • a preferred pH range is 7.0 to 10.0.
  • the pH may be adjusted by adding a base or an acid.
  • any suitable base or acid may be used, however non-limiting examples of suitable bases are alkali or earth metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, or ammonia, amines, or carbonates such as sodium carbonate, or butyl lithium, sodium amide or sodium hydride.
  • suitable acids are sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, benzoic acid, citric acid, formic acid and acetic acid.
  • the pH is preferably 6.0 to 1 1, more preferably 7.0 to 9.0.
  • the sulfur containing reducing agent may be added in a 1:2 to 2: 1, or a 1: 1.5 to 1.5: 1, or a 1 : 1.2 to 1.2: 1, or a 1 : 1 molar ratio to the repeating unit of lignin or lignin derivatives.
  • a 1 : 1.5 to 1.5: 1, or a 1 : 1.2 to 1.2: 1, or a 1 : 1 molar ratio to the repeating unit of lignin or lignin derivatives.
  • M w weight average molecular weight
  • the amount is essentially stoichiometric to the amount of lignin based on a molecular weight of the lignin.
  • the sulfur containing reducing agent may be a dithionite, sulfite, thiosulphate, metabisulfite, sulfinate, thiourea, thiourea oxide, thiourea dioxide, thiourea trioxide, hydroxylm ethane sulfinate, hydroxyethane sulfinate, hydroxypropane sulfinate, hydroxybutane sulfinate, thiophenol or sulfur dioxide, a non-limiting list of sulfur containing agents is sodium or potassium dithionite, sodium or potassium hydroxymethane sulfinate, sodium or potassium sulfite, sodium or potassium bisulfite, or any combination thereof.
  • the agent is ditionite.
  • the agent is a sulfite.
  • the agent is a thiosulph
  • the agent is selected from sodium dithionite, sodium or potassium sulfite, sodium hydroxymethane sulfinate or thiourea oxides.
  • the sulfur containing reducing agent is a sulfite or a sulfite forming agent.
  • the reaction may be performed at a temperature of 20°C or higher, or 40°C or higher, or 60°C or higher, or 80°C or higher, or 100°C or higher, or 120°C or higher.
  • One preferred temperature range at which the mixture may be heated at is 60- 160°C, or 100 to 150°C.
  • the reaction may be performed during reflux.
  • the depolymerization reaction may continue for 1 hour or longer, or 3 hours or longer, or 6 hours or longer, or 12 hours or longer and may be performed in an inert atmosphere or in an atmosphere containing inert gas.
  • the mixture may be stirred or shaken prior to or during the depolymerization reaction.
  • the reaction may be performed at an elevated pressure such as 2 bar or higher, or 4 bar or higher. The elevated pressure may be obtained by performing the reaction in a sealed container.
  • the amount of water is preferably large enough to keep the depolymerized lignin in solution. If the amount of water is too low the lignin will precipitate during the depolymerization which will lead to less effective mixing and less effective reaction conditions.
  • the weight ratio of water to lignin may be 5.1 or higher, such as 10: 1 or higher, or 20: 1 or higher.
  • the obtained depolymerized lignin may have a weight average molecular weight of 400- 1000 g/mol, for example 500-900 g/mol.
  • the polydispersity index of the depolymerized lignin according to the present invention may be around 1.3 to 2.0.
  • Molecular weight in the present application is determined using GPC (Gel
  • composition according to the present invention comprises depolymerized lignin, and a carrier liquid and / or an organic solvent.
  • the amount of depolymerized lignin or lignin derivatives in the composition may be 1 weigh t% or more, or 4 weight% or more, or 5 weight% or more, or 7 weight% or more, or 10 weight% or more, or 12 weight% or more, or 15 weight% or more, or 20 weight% or more, or 25 weight% or more, or 30 weight% or more, or 40 weight% or more, or 50 weight% or more, or 60 weight% or more, or 70 weight% or more, or 75 weigh t% or more.
  • the depolymerized lignin or lignin derivatives are dearomatized.
  • lignin or lignin derivatives are dearomatized to at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 99%.
  • the purpose of the carrier liquid is to carry the wanted substrate or solution into the reactor without reacting or in any other way affecting the substrate or solution. Therefore, in the present application a carrier liquid is an inert hydrocarbon with a high boiling point, preferably at least 150°C.
  • the carrier liquid is a fatty acid or a mixture of fatty acids.
  • the carrier liquid is esterified fatty acids such as FAME (fatty acid methyl ester).
  • the carrier liquid is a crude oil.
  • the carrier liquid is bunker fuel or bunker crude. In another embodiment the carrier liquid is a hydrocarbon oil or a mineral oil. In one embodiment the carrier liquid is a mixture of esterified fatty acid and an mineral oil, hydrocarbon oil, bunker fuel or crude oil. In another
  • the carrier liquid is a mixture of a hydrocarbon oil or a mineral oil and a fatty acid.
  • Bunker fuel or bunker crude are fuel mainly used for ships, usually very large ships.
  • the bunker fuel may be divided into groups depending on if the fuel is a distillate or a residual or a mixture of both and the chain length.
  • No. 1 fuel oil is a distillate with a chain length of 9-16
  • No. 2 fuel oil also known as
  • Bunker A is a distillate with a chain length of 10-20
  • No. 4 and No. 5 fuel oil also known as Bunker B
  • Bunker C is a distillate and a residual oil respectively with a chain length of 12-70
  • No. 6 fuel oil also known as Bunker C
  • No. 5 and 6 are also known as heavy fuel oil (HFO) or furnace fuel oil (FFO).
  • the bunker fuel is a Bunker B.
  • the bunker fuel is a HFO or Bunker C.
  • the carrier liquid should preferably be suitable for a hydrotreater or a catalytic cracker (cat cracker), preferably a liquid suitable for both hydrotreater and catalytic cracker.
  • Hydrotreater and catalytic cracker are steps in the refinery process where for example the sulfur content of the oil is reduced and where high-boiling, high molecular weight hydrocarbons are converted into gasoline, diesel and gases.
  • hydrotreaters common catalysts are cobalt-molybdenum for removing sulfur and for olefin saturation, and nickel-molybedenum for removing nitrogen and aromatic saturation.
  • catalytic crackers may crystalline silica alumina be used with a metal deposit where the metal may be platinum, palladium, tungsten, nickel or rare earth metals.
  • the carrier liquid content may be at least 5 weight%, or at least 10 weight%, or at least 20 weight%, or at least 30 weight%, or at least 40 weight%, preferably at least 50 weight%, but preferably less than 90 weight%, or less than 80 weight%, or less than 70 weight%, or less than 60 weight%, or less than 55 weight%.
  • the carrier liquid is a fatty acid or a mixture of fatty acids.
  • the fatty acid or the mixture of the fatty acids comprises unsaturated fatty acids, preferably at a concentration of more than 25 wt%, or more than 50 wt%.
  • the carrier liquid is a tall oil.
  • the carrier liquid is a hydrocarbon oil or a mineral oil.
  • the carrier liquid is a mixture of a fatty acid and a hydrocarbon oil or a mineral oil. The ratio in said mixture may be 10-90 wt% fatty acid and 10-90 wt% of hydrocarbon oil or mineral oil, for example 20-40 wt% fatty acid and 60-80 wt% of hydrocarbon oil or mineral oil.
  • the carrier liquid is or comprises a hydrocarbon oil
  • the oil needs to be in liquid phase below 80 °C and preferably have boiling points of 177-371 °C.
  • hydrocarbon oils include different types of or gas oils and likewise e.g. Full Range Straight Run Middle Distillates, Hydrotreated, Middle Distillate, Light Catalytic Cracked Distillate, distillates Naphtha full-range straight-run, Distillates, hydrodesulfurized full-range, Distillates, solvent-dewaxed straight-range,
  • compositions according to the present invention may comprise a solvent or a mixture of solvents.
  • the solvent may be an organic solvent or a mixture of organic solvents.
  • the solvent is a mixture of an organic solvent and a carrier liquid.
  • the organic solvent may be but is not limited to oxygenates such as an alcohol, ester, ketone, ether, aldehydes, furan or furfural based solvent.
  • Preferred solvents are C1-C10 alcohols, C1-C10 aldehydes, C2-C15 ketones, C2-
  • C10 ethers and C2-C10 esters.
  • solvents is methanol, ethanol, propanol, isopropanol, glycerol, and butyl ether such as tert-butyl methyl ether; diethyl ether, diglyme, diisopropyl ether, dimethoxyethane, diethylene glycol, diethyl ether, polyethylene glycol, 1,4-dioxane and tetrahydrofuran, methylated
  • C2-C10 esters are organic esters, aromatic or non-aromatic esters, examples of esters are benzyl benzoate, various acetates such as methyl acetate, ethyl acetate, cyclopentyl methyl ether and butyl acetate, various lactates such as ethyl lactates.
  • Solvents that are similar to or may be converted into fuel or petrol are interesting when the
  • composition is to be used for fuel preparation.
  • solvents could be ketones or aldehydes.
  • the solvent is a C2-C15 ketone such as a C4-C12 ketone or a C6-C8 ketone.
  • the solvent is a C1-C10 aldehyde such as a C4-C9 aldehyde or C6-C8 aldehyde.
  • the solvent is a mixture of a C2-C15 ketone and a CI -CIO aldehyde.
  • the solvent is mesityl oxide.
  • the solvent is acetone.
  • the solvent is acetophenone.
  • the solvent is pentanone.
  • the solvent is ethyl isopropyl ketone. In one embodiment the solvent is isophorone. In one embodiment the organic solvent is an aromatic aldehyde or a mixture containing an aromatic aldehyde for example furfural. In one embodiment the solvent comprises furfural or furfuryl alcohol. In one embodiment the solvent is benzaldehyde. In one embodiment the solvent is ethyl acetate. In one embodiment the solvent is a C1-C10 alcohol. In one embodiment the solvent is ethanol. In one embodiment the solvent is methanol. In one embodiment the solvent is is isopropanol. In one embodiment the solvent is solketal. In one embodiment the solvent is a C2- CIO ester. In one embodiment the solvent is tetrahydrofuran or methylated tetrahydrofuran. In one embodiment the solvent is 1,4-dioxane.
  • the solvent comprises a combination of C1-C10 alcohols, C2- C10 ethers and C2-C10 esters.
  • the solvent comprises two Cl- C10 alcohols for example ethanol and glycerol, and in another embodiment the solvent comprises propanol and glycerol.
  • the solvent comprises polyethylene glycol and a C1-C10 alcohol.
  • the solvent is a mixture of an organic solvent and water the mixture may contain methanol and water, ethanol and water, isopropanol and water or ethyl acetate and water, preferably ethanol and water, isopropanol and water and ethyl acetate and water.
  • the solvent is a mixture of a C2-C15 ketone such as a C4-C12 ketone or a C6-C8 ketone or a C1-C10 aldehyde such as a C4-C9 aldehyde or C6- C8 aldehyde and a carrier liquid.
  • the solvent is a mixture of a C1-C10 alcohol such as a C3-C8 alcohol and a carrier liquid.
  • the amount of organic solvent in the composition is 1-99 weight% of the total weight of the composition. In one embodiment the amount of solvent is 10-60 weight%, or 20-50 weight%. In one embodiment the amount of organic solvent is70 weight% or less, or 40 weight% or less, or 20 weight% or less, or 10 weight% or less, or 5 weight% or less, or 2 weight% or less of the total weight of the composition.
  • the composition may further comprise at least one additive.
  • the additive may be any additive known to a person skilled in the art.
  • the additive may further enhance the dissolution of the lignin or lignin derivatives.
  • the additive may have the function of dissolving or breaking up inter molecular bonds between the lignin chains or the lignin derivatives.
  • the additive is a polar compound or a salt.
  • the composition according to the present invention may be prepared by first depolymerizing the lignin or lignin derivatives according to the present invention.
  • the depolymerized lignin or lignin derivatives may be isolated prior to further treatment or prior to mixing with the other components of the composition.
  • the depolymerized lignin or lignin derivatives may be dissolved in a suitable solvent and then mixed with a carrier liquid to the wanted lignin content.
  • the lignin may be esterified.
  • the esterified biomass may be isolated from the esterification reaction mixture or the esterified biomass is left in the reaction mixture when mixed with the carrier liquid.
  • the esterification of the biomass may also be performed in situ, i.e. in the carrier liquid.
  • the biomass, the esterification agent or, the first fatty acid and an esterification agent, and the carrier liquid and optionally a catalyst are mixed to form a slurry.
  • the slurry is then preferably heated for example to 80°C or higher, or 120°C or higher.
  • the esterification of the biomass occurs in the carrier liquid leaving a homogenous composition of carrier liquid and esterified biomass, and optionally catalyst.
  • the catalyst and any other unwanted components may be removed afterwards.
  • the mixing can be done by stirring or shaking or in any other suitable way.
  • esterification is performed in a carrier liquid comprising a first fatty acid and together with an esterification agent such as an anhydride the obtained esterified lignin is believed to comprise ester groups derived from the anhydride alone but also ester groups derived from an anhydride bond to a first fatty acid.
  • the esterified lignin may be isolated by precipitation in for example hexane or water.
  • degree of substitution for example 50% or more
  • the esterified lignin may be treated with a base for example NaHC03 (aq-) before precipitation in order to remove free acid.
  • a base for example NaHC03 (aq-)
  • celite may be used.
  • One way of precipitating the depolymerized lignin is by adding SO 2 to the reaction, for example by bubbling SO 2 into the reaction. The precipitated lignin may then be isolated using any suitable technique.
  • the esterified lignin according to the present invention may also be separated from metals and other additives or catalysts by simply rinsing the lignin in an aqueous solution or water.
  • processing lignin the amount of metals should be as low as possible since metals may damage the machinery or disturb the process.
  • ester groups in situ insoluble biomass may become soluble.
  • lignin substituted with acetic ester groups is not dissolved in tall oil.
  • the mixing may be performed at room temperature, but may be performed at a temperature between 50°C and 350°C, such as 50°C or higher, or 80°C or higher or 100°C or higher, or 120°C or higher, or 150°C or higher, but not higher than 350°C, or 250°C or lower, or 200°C or lower, or 180°C or lower.
  • 50°C or higher such as 50°C or higher, or 80°C or higher or 100°C or higher, or 120°C or higher, or 150°C or higher, but not higher than 350°C, or 250°C or lower, or 200°C or lower, or 180°C or lower.
  • the esterification agent may be a carboxylic acid or an anhydride.
  • the esterification agents preferably contain an unsaturated bond.
  • carboxylic acids are fatty acids or C2-C40 carboxylic esters, preferably C4 to C22.
  • Non-limiting examples of anhydrides are C4 to C42 anhydrides.
  • the catalyst may be a nitrogen containing aromatic heterocycle such as N-methyl imidazole or pyridine.
  • the catalyst may also be titanium based catalyst or an iron catalyst.
  • the carrier liquid is a fatty acid (second fatty acid) said fatty acid may be but is not limited to C6-C18 fatty acids, saturated or unsaturated, or a mixtures of C2- C18 fatty acids.
  • the second fatty acid may further be methylated or ethylated.
  • the second fatty acid may be a vegetable fatty acid such as a tall oil, or olive oil, soybean oil, corn oil, hemp or coconut oil.
  • the first and the second fatty acid are the same.
  • the carrier liquid is a second fatty acid or a mixture of second fatty acids or a mixture comprising a second fatty acid.
  • the second fatty acid is an unsaturated fatty acid or is a mixture of fatty acids in which the mixture contains unsaturated fatty acids.
  • the first and the second fatty acids are the same, for example tall oils.
  • the composition comprises a first fatty acid or oil and lignin or lignin derivatives; wherein at least one of the hydroxyl groups of the lignin or lignin derivatives have been substituted with an ester groups of a second fatty acid, preferably an unsaturated second fatty acid, forming esterified lignin or lignin derivatives.
  • the degree of substitution i.e.
  • the degree of hydroxyl groups that has been converted into ester groups may be from 10% to 100%, for example 20% or more, 30% or more, or 40% or more, or 60% or more or 80% or more, or 99% or more, or 100%. It is also possible to have part of the lignin, or the hydroxyl groups on the lignin, being substituted with one type of ester group (for example C2-C6 ester groups) and another part substituted with another type of ester group (for example C8-C18 ester groups). For example 10-40 % of the hydroxyl groups may be substituted with acetyl groups and 60-90% of the hydroxyl groups may be substituted with a fatty acid, preferably C12 or longer ester groups.
  • Fully or near fully substituted (degree of substitution of 100% or near 100%) lignin wherein the ester group is unsaturated is an oil at room temperature while lignin substituted with a saturated ester group is a solid or wax like material.
  • lignin substituted with a saturated ester group is a solid or wax like material.
  • the lignin becomes soluble in ethyl acetate, methyl THF, cyclopentyl methyl ether and iso-propanol. This is especially pronounced for C4 or longer ester groups. It is even more pronounced when the ester group is a C6 or longer chain, preferably C8 or longer, or C12 or longer, preferably C14 or longer chain.
  • the degree of substitution may preferably be more than 30% for ester groups of C8 and longer, preferably 50% or more. If the carrier liquid is a mixture of a fatty acid and an oil the esterified lignin becomes more soluble.
  • the non-esterified groups may be capped for example with an anhydride such as acetic anhydride under common esterification conditions.
  • One advantage of the present invention is that a higher amount of lignin may be dissolved in a carrier liquid.
  • the amount of lignin or lignin derivatives in the composition according to the present invention may be 4 weight% or more, or 5 weight% or more, or 7 weight% or more, or 10 weight% or more, or 12 weight% or more, or 15 weight% or more, or 20 weight% or more, or 25 weight% or more, or 30 weight% or more, or 40 weight% or more, or 50 weight% or more, or 60 weight% or more, or 70 weigh t% or more, or 75 weight% or more.
  • the liquor may be pre-treated by evaporation, separation or filtration or via chemical treatments such as the process described below and further defined in
  • the biomass material in the composition may have been treated with the process described in WO2012/ 121659 which is hereby incorporated by reference.
  • the process relates to reduction of a substrate wherein said substrate can be but is not limited to primary, secondary and tertiary benzylic or allylic alcohol, benzylic or allylic ether, benzylic or allylic carbonyl, and benzylic or allylic ester, or olefins to the corresponding hydrocarbon.
  • the substrate may be lignin or any other
  • a general method comprises adding a catalyst, a transition metal catalyst, to a reaction flask or container. Adding a solvent mixture of at least two solvents where one of the solvents is water and a base. The mixture is then heated followed by addition of a hydrogen donor and the substrate to be reduced. In order to inhibit disproportionation, a base or carbon dioxide should be added to the solvent mixture and catalyst prior to addition of a hydrogen donor and the substrate.
  • the hydrogen donor may for example be formic acid or an alcohol, it may even be hydrogen gas.
  • the reduction is performed at a temperature of 40- 100°C. In one embodiment the amount of base is not stoichiometric to the amount of the substrate.
  • the biomass material or preferably the separated lignin and lignin derivatives obtained from the reduction method may then be used as the biomass material in the composition according to the present invention.
  • the obtained biomass material from the chemical reduction is further treated with filtration, ultrafiltration or cross-flow ultra-filtration; or treated with acidification and separation such as the Lignoboost® technique for example as described in WO2006/031175.
  • lignin and lignin derivatives for example by acidification and separation, such as filtration. Lignoboost® or any other similar separation technique are examples of such technique and may be used.
  • the separated lignin and lignin derivatives may then be used as the biomass material in the composition according to the present invention.
  • the separated lignin and lignin derivative may further be chemically reduced using the method described above and in WO2012/ 121659.
  • Another method or a complimentary method for purifying or separating specific components in a biomass material is through filtration, ultra-filtration or cross-flow ultra-filtration.
  • the biomass material comprises lignin or lignin derivatives
  • the lignin may be separated in respect to size through any of said filtration techniques.
  • the lignin or lignin derivatives may also be separated in respect to size through a depolymerisation technique; this separation may be performed in combination with filtration, ultra-filtration or cross-flow ultra-filtration.
  • lignin or lignin derivatives with molecular weights of 10,000 g/mol or less may be separated, preferably the separated lignin or lignin derivatives have a molecular weight of 2,000g/mol or less, such as 1 ,000 g/mol or less.
  • the separated lignin and lignin derivatives may then be used as the biomass material in the composition according to the present invention.
  • the lignin and lignin derivatives obtained from said filtration may further be chemically reduced using the method described above and in WO2012/ 121659.
  • the lignin may also be extracted using an appropriate solvent such an alcohol for example methanol, ethanol or iso-propanol.
  • composition according to the present invention may be used in a refinery process or as a pre-step to a refinery process for preparing fuel such as diesel and petrol, or diesel and petrol analogues; or biogasoline or biodiesel; or fuel additives.
  • fuel such as diesel and petrol, or diesel and petrol analogues; or biogasoline or biodiesel; or fuel additives.
  • Any hydrotreatment or hydroprocessing may be used, and any catalytic cracking process may be used.
  • the composition is hydrotreated prior to the catalytic cracking.
  • composition according to the present invention may also be used as an additive, for example as a concreted grinding aid, set retarder for cement, strengthener of cement, antioxidant, enhancer of thermal protection, stabilizer in asphalt, emulsifying agent, fiber strengthening additive, cross-linking agent, board binder, anti-corrosion additive, wear resistant additive, antifriction additive, binder, emulsifier or dispersing agent.
  • the composition may further be used to prepare foams, plastics, rubbers or paint.
  • the esterified lignin may be used as a cross-linking or curing agent, or as a water absorption inhibitor or as a fluidization agent. Mechanical properties may also be enhanced by the use of the composition.
  • the composition and the method set retarder for cement, strengthener of cement, antioxidant, enhancer of thermal protection, stabilizer in asphalt, emulsifying agent, fiber strengthening additive, cross-linking agent, board binder, anti-corrosion additive, wear resistant additive, antifriction additive, binder, emulsifier or dispersing
  • composition may be added to surfaces to obtain dust control, or the
  • composition may be used to prepare batteries.
  • Kraft lignin (0.50 g, 2.78 mmol of repeating unit), Na 2 S 2 0 4 (0.73 g, 4.19 mmol), water (5 ml) and NaOH (0.16 g) were loaded into a microwave vial with a magnet.
  • the vial was capped, purged with argon and heated at 140 °C for 21 h.
  • the reaction was cooled to room temperature, diluted with water (5 ml) and tetrahydrofuran (5 ml), and acidified with cone. HC1. After phase separation the aqueous phase was further extracted with tetrahydrofuran (10 ml).
  • the combined organic extracts were washed with brine (20 ml) and dried over Na 2 S0 4 . Evaporation of solvents afforded 0.31 g of brown solid.
  • Example 2 As in example 1 , following amounts were used: kraft lignin (0.50 g), Na2S203 (0.66 g), water (5 ml) and NaOH (0.16 g). The reaction proceeded for 19 h.
  • Example 5 As in example 1 , following amounts were used: kraft lignin (0.10 g), Na2S03 (0.28 g), water (2 ml) and NaOH (62 mg), pH around 14. The reaction proceeded for 19 h.
  • Kraft lignin (10.00 g) and Na2S03 (5.25 g) were suspended in water (100 ml).
  • Example 9 Water (5ml) was added to a reaction flask containing Lignoboost® lignin with a dryness of 95% (0.5g, 2.8mmol), sodium hydroxide (0.18g, 4.5mmol) and sodium dithionite (0.37g, 2.1mmol). The flask was sealed and heated during stirring for 5 days at 150°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken, and diluted with THF, for GPC-analysis (figure 2).
  • Example 10 Water (5ml) was added to a reaction flask containing Lignoboost® lignin with a dryness of 95% (0.503g, 2.8mmol), sodium hydroxide (0.306g, 7.6mmol) and sodium dithionite (3.189g, 18.3mmol). The flask was sealed and heated during stirring for 3 days at 1 10°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken and diluted with THF, neutralized with HC1 filtered and then injected on GPC (figure 3).
  • Example 12 Lignoboost® lignin with a dryness of 95% was extracted using isopropanol in order to obtain lignin large fractions ("large fraction lignin”). The lignin was isolated using filtration. Water (5ml) was added to a reaction flask containing "large fraction lignin” (0.504g, 2.8mmol), sodium hydroxide (0.127g, 3.2mmol) and sodium dithionite (0.725g, 4.2mmol). The flask was sealed and heated during stirring for 24h at 140°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken and injected on GPC (figure 4).
  • Example 15 Lignoboost® lignin with a dryness of 95% was extracted using isopropanol in order to obtain lignin large fractions. The lignin was isolated using filtration. Water (5ml) was added to a reaction flask containing "lignin large fractions" (0.5g, 2.8mmol), sodium hydroxide (0.182g, 4.6mmol) and sodium dithionite (0.0487g, 0.28mmol, 0.1 eq). The flask was sealed and heated during stirring for 24h at 140°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken, diluted with THF and injected on GPC (figure 6).
  • Lignoboost® lignin with a dryness of 95% was extracted using isopropanol in order to obtain lignin large fractions.
  • the lignin was isolated using filtration. Water (5ml) was added to a reaction flask containing "lignin large fractions" (0.5g, 2.8mmol), sodium hydroxide (0.159g, 3.9mmol) and sodium dithionite (0.146g, 0.84 mmol, 0.3 eq.). The flask was sealed and heated during stirring for 24h at 140°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken, diluted with THF and injected on GPC (figure 6).
  • Lignoboost® lignin with a dryness of 95% was extracted using isopropanol in order to obtain lignin large fractions.
  • the lignin was isolated using filtration. Water (5ml) was added to a reaction flask containing "lignin large fractions" (0.5g, 2.8mmol), sodium hydroxide (0.171g, 4.2mmol) and sodium dithionite (0.292g, 1.7mmol, 0.6eq). The flask was sealed and heated during stirring for 24h at 140°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken, diluted with THF and injected on GPC (figure 6).
  • Lignoboost® lignin with a dryness of 95% was extracted using isopropanol in order to obtain lignin large fractions.
  • the lignin was isolated using filtration. Water (5ml) was added to a reaction flask containing "lignin large fractions" (0.5g, 2.8mmol), sodium hydroxide (0.177g, 4.4mmol) and sodium dithionite (0.439g, 2.5mmol, 0.9eq). The flask was sealed and heated during stirring for 24h at 140°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken, diluted with THF and injected on GPC (figure 6).
  • Lignoboost® lignin with a dryness of 95% was extracted using isopropanol in order to obtain lignin large fractions.
  • the lignin was isolated using filtration. Water (5ml) was added to a reaction flask containing "lignin large fractions" (0.5g, 2.8mmol), sodium hydroxide (0.173g, 4.3mmol) and sodium dithionite (0.5846g, 3.4mmol, 1.2eq). The flask was sealed and heated during stirring for 24h at 140°C. After cooling THF (2ml) was added and stirred until all precipitated material had dissolved ( ⁇ lh). A homogeneous sample was taken, diluted with THF and injected on GPC (figure 6).
  • a microwave (MW)-vial was loaded with kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S 2 0 4 (0.73 g, 1.5 eq, 4.19 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4,0 mmol).
  • the vial was heated at 140 °C for 20 hours. After cooling, water (5 ml) and THF (10 ml) were added.
  • the solution was acidified with concentrated HC1 and an aqueous phase and an organic phase were formed.
  • the aqueous phase was extracted with THF (10 ml).
  • the combined organic phase was washed with brine (10 ml), dried over Na 2 S0 4 and solvent was evaporated to afford 0.31 g product.
  • Example 21 The reaction was performed as in Example 20 with the following amounts: kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S 2 0 3 (0.66 g, 1.5 eq, 4.17 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4.0 mmol). After the same work up as in Example 20 the product was analysed by GPC.
  • Example 22 The reaction was performed as in Example 20 with the following amounts: kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S0 3 (0.53 g, 1.5 eq, 4.21 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4.0 mmol). After the same work up as in Example 20 the product was analysed by GPC.
  • Example 23 kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S0 3 (0.53 g, 1.5 eq, 4.21 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4.0 mmol). After the same work up as in Example 20 the product was analysed by GPC.
  • Example 23 The reaction was performed as in Example 20 with the following amounts: kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S0 3 (0.53 g, 1.5 eq
  • Example 20 The reaction was performed as in Example 20 with following amounts: kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S 2 0 3 (0.22 g, 0.5 eq, 1.39 mmol), Na 2 S0 3 (0.35 g, 1 eq, 4.21 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4.0 mmol). After the same work up as in Example 20 the product was analysed by GPC.
  • Example 20 The reaction was performed as in Example 20with following amounts: kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S0 3 (0.35 g, 1 eq, 2.78 mmol), Na 2 S 2 0 5 (0.26 g, 0.5 eq, 1.37 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4.0 mmol). After the same work up as in Example 20 the product was analysed by GPC.
  • Example 20 The reaction was performed as in Example 20 with following amounts: kraft lignin (0.50 g, 1 eq, 2.78 mmol), Na 2 S 2 0 5 (0.40 g, 0.75 eq, 2.10 mmol), water (5 ml) and NaOH (0.16 g, ca 1.5 eq, 4.0 mmol). After the same work up as in Example 20 the product was analysed by GPC.
  • Example 28 As a reference test sulfuric acid was used in the following example. A solution of 50% black liquor (4.00 g) and water (10 ml) was neutralised (pH 7.0) with H 2 S0 4 and heated at 140 °C for 18 hours. After a similar work up as in Example 20 the product was analysed by GPC, no depolymerization was seen.
  • Example 28 As a reference test carbon dioxide was used in the following example. A solution of 50% black liquor (4.00 g) and water (10 ml) was neutralised (pH 7.3) with C02(g) and heated at 140 °C for 18 hours. After a similar work up as in Example 20 the product was analysed by GPC, no depolymerization was seen.

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Abstract

La présente invention concerne un procédé de dépolymérisation de lignine comprenant les étapes consistant à fournir une solution aqueuse contenant de la lignine et à ajouter un agent réducteur contenant du soufre à la solution pour former un mélange, et à chauffer de préférence le mélange formé. L'agent réducteur est ajouté selon un rapport molaire de 1:2 à 2:1 par rapport à l'unité de répétition de la lignigne.
PCT/SE2015/050745 2014-06-27 2015-06-25 Dépolymérisation de lignine WO2015199608A1 (fr)

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WO2019081819A1 (fr) * 2017-10-26 2019-05-02 Aalto University Foundation Sr Dispersions aqueuses de lignine et procédés de préparation associés
WO2020089521A1 (fr) * 2018-10-31 2020-05-07 Upm-Kymmene Corporation Composition de biodiesel
WO2021058483A1 (fr) 2019-09-23 2021-04-01 Université Catholique de Louvain Procédé de production de composants de lignine à partir de biomasse lignocellulosique

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US20020129910A1 (en) * 2001-03-14 2002-09-19 Lightner Gene E. Separation of black liquor to produce lignins substantially free of sodium
US20030221804A1 (en) * 2002-06-03 2003-12-04 Lightner Gene E. Lignins derived from black liquor
WO2013130101A1 (fr) * 2012-03-02 2013-09-06 Empire Technology Development Llc Dérivés de lignine et leurs utilisations
WO2013135485A1 (fr) * 2012-03-12 2013-09-19 Brandenburgische Technische Universität Cottbus Procédé de fabrication d'agglomérats de lignine insolubles dans l'eau

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Publication number Priority date Publication date Assignee Title
US20020129910A1 (en) * 2001-03-14 2002-09-19 Lightner Gene E. Separation of black liquor to produce lignins substantially free of sodium
US20030221804A1 (en) * 2002-06-03 2003-12-04 Lightner Gene E. Lignins derived from black liquor
WO2013130101A1 (fr) * 2012-03-02 2013-09-06 Empire Technology Development Llc Dérivés de lignine et leurs utilisations
WO2013135485A1 (fr) * 2012-03-12 2013-09-19 Brandenburgische Technische Universität Cottbus Procédé de fabrication d'agglomérats de lignine insolubles dans l'eau

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019081819A1 (fr) * 2017-10-26 2019-05-02 Aalto University Foundation Sr Dispersions aqueuses de lignine et procédés de préparation associés
US11524974B2 (en) 2017-10-26 2022-12-13 Aalto University Foundation Sr Aqueous lignin dispersions and methods of preparing the same
WO2020089521A1 (fr) * 2018-10-31 2020-05-07 Upm-Kymmene Corporation Composition de biodiesel
JP2022504811A (ja) * 2018-10-31 2022-01-13 ユー ピー エム キュンメネ コーポレーション バイオディーゼル組成物
US11434442B2 (en) 2018-10-31 2022-09-06 Upm-Kymmene Corporation Biodiesel composition
JP7510410B2 (ja) 2018-10-31 2024-07-03 ユー ピー エム キュンメネ コーポレーション バイオディーゼル組成物
WO2021058483A1 (fr) 2019-09-23 2021-04-01 Université Catholique de Louvain Procédé de production de composants de lignine à partir de biomasse lignocellulosique

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