SE537732C2 - Composition comprising fatty acids and esters of lignin - Google Patents

Composition comprising fatty acids and esters of lignin Download PDF

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Publication number
SE537732C2
SE537732C2 SE1351508A SE1351508A SE537732C2 SE 537732 C2 SE537732 C2 SE 537732C2 SE 1351508 A SE1351508 A SE 1351508A SE 1351508 A SE1351508 A SE 1351508A SE 537732 C2 SE537732 C2 SE 537732C2
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lignin
ester
fatty acid
so1ution
composition
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SE1351508A
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Swedish (sv)
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SE1351508A1 (en
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Joseph Samec
Joakim Löfstedt
Christian Dahlstrand
Alexander Paptchikine
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Ren Fuel K2B Ab
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Application filed by Ren Fuel K2B Ab filed Critical Ren Fuel K2B Ab
Priority to SE1351508A priority Critical patent/SE537732C2/en
Priority to RU2016125714A priority patent/RU2690503C1/en
Priority to CA2933841A priority patent/CA2933841A1/en
Priority to CN201480074489.5A priority patent/CN106132976B/en
Priority to US15/104,702 priority patent/US10030147B2/en
Priority to EP21182866.0A priority patent/EP3910029A1/en
Priority to BR112016013916-0A priority patent/BR112016013916B1/en
Priority to SG11201604775TA priority patent/SG11201604775TA/en
Priority to EP14870806.8A priority patent/EP3083652B1/en
Priority to CA2933848A priority patent/CA2933848C/en
Priority to US15/104,664 priority patent/US20160312029A1/en
Priority to EP14872144.2A priority patent/EP3083653A4/en
Priority to PCT/SE2014/051507 priority patent/WO2015094099A1/en
Priority to CN201480074490.8A priority patent/CN106164084A/en
Priority to DK14870806.8T priority patent/DK3083652T3/en
Priority to PCT/SE2014/051506 priority patent/WO2015094098A1/en
Priority to PT14870806T priority patent/PT3083652T/en
Priority to BR112016013905A priority patent/BR112016013905A2/en
Priority to JP2016559143A priority patent/JP6525343B2/en
Priority to ES14870806T priority patent/ES2895101T3/en
Priority to JP2016559142A priority patent/JP2017501290A/en
Priority to CN201910052890.3A priority patent/CN110079365B/en
Priority to PL14870806T priority patent/PL3083652T3/en
Publication of SE1351508A1 publication Critical patent/SE1351508A1/en
Publication of SE537732C2 publication Critical patent/SE537732C2/en
Priority to CL2016001542A priority patent/CL2016001542A1/en
Priority to US16/014,271 priority patent/US10421861B2/en
Priority to US16/540,111 priority patent/US10781313B2/en

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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
    • C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • 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
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • 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
    • 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
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • C11B13/005—Recovery of fats, fatty oils or fatty acids from waste materials of residues of the fabrication of wood-cellulose (in particular tall-oil)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

28 ABSTRACT The present invention re1ates to a composition With a high lignin content in a fattyacid or oi1 Where the lignin has been functionalized With acyl groups and a method of preparing said composition Where the acylation step may be performed in the fatty acid or oil.

Description

The present invention relates to a composition With a high lignin content in asolvent such as an organic solvent, fatty acid or oil where the lignin has beenfunctionalized with ester groups and a method of preparing said composition wherethe esterf1cation step may be performed in the fatty acid or oil. The composition may be used to produce fuels.BACKGROUND There is an increasing interest in using biomass as a source for fuel production.Biomass includes, but is not limited to, plant parts, fruits, vegetables, processingwaste, wood chips, chaff, grain, grasses, com, com husks, Weeds, aquatic plants,hay, paper, paper products, recycled paper and paper products, lignocellulosicmaterial, 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 thebiomass. Lignin comprises chains of aromatic and oxygenate constituents forminglarger molecules that are not easily treated. A major reason for difficulty in treatingthe 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 ofpreparing lignin is by separation from wood during pulping processes. Only a smallamount (1-2 %) is utilized in specialty products whereas the rest primary serves asfuel. Even if burning lignin is a valuable way to reduce usage of fossil fuel, ligninhas significant potential as raw material for the sustainable production of chemicals and fuel.
Various lignins differ structurally depending on raw material source andsubsequent processing, but one common feature is a backbone consisting ofvarious substituted phenyl propane units that are bound to each other via arylether or carbon-carbon linkages. They are typically substituted with methoXylgroups 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.
Today lignin may be used as a component in for example pellet fuel as a binder butit may also be used as an energy source due to its high energf content. Lignírl han;higher) energy' content; than eelluítuse or l1ern.if:ell1;f.lï>ses amd one grarn of lígznít: hanen :average 2.'L2'i” KJ, mfhiclw 30941 more tlfiaærx. tlfie energy contfiïnt of celíulosicearlaohgfdrate. Tlïe energy content of lignin is sirnílar to thzat of Goal. 'Fcdayy due toits ftlel value lígiïin thzat has been rerncwecl using the kraft process, sttlpllateprocess, in a 'gßulgu :är pagæer xníll, is usually lßurned in ordet' to prc-*Jícle energy to run the p1'<';fluc,tí<_>r1 process and to recoxfer the tzherníatals fmtrt the (Jooläírlg lic¿t':.o1:".
There are several ways of separating lignin from black or red liquor obtained afterseparating the cellulose f1bres in the kraft or sulphite process respectively, duringthe production processes. One of the most common strategies is ultra-filtration.Lignoboost® is a separation process developed by Innventia AB and the process hasbeen shown to increase the lignin yield using less sulphuric acid. In theLignoboost® process, black liquor from the production processes is taken and thelignin is precipitated through the addition and reaction With acid, usually carbondioXide (C02), and the lignin is then filtered off. The lignin filter cake is then re-dispersed and acidified, usually using sulphuric acid, and the obtained slurry isthen filtered and washed using displacement washing. The lignin is usually thendried 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, is a fuel in which the energi is mainlyderived from biomass material or gases such as wood, corn, sugarcane, animal fat,vegetable oils and so on. However the biofuel industries are struggling with issueslike food vs fuel debate, efficiency and the general supply of raw material. At thesame time the pulp or paper making industries produces huge amounts of ligninwhich is often, as described above, only burned in the mill. Two common strategiesfor exploring biomass as a fuel or fuel component are to use pyrolysis oils or hydrogenated lignin.
In order to make lignin more useful one has to solve the problem with the lowsolubility 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 hydro treaters 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 ormolecules in order to prepare lignin derivatives that may be processed. Thesestrategies include hydrogenation, dexoygenation and acid catalyst hydrolysis.WO2011003029 relates to a method for catalytic cleavage of carbon-carbon bondsand carbon-oxygen bonds in lignin. US20130025191 relates to a depolymerisationand deoXygenation method where lignin is treated with hydrogen together With acatalyst in an aromatic containing solvent. All these strategies relates to methodswhere the degradation is performed prior to eventual mixing in fatty acids or oils.WO2008157164 discloses an alternative strategy where a first dispersion agent isused to form a biomass suspension to obtain a better contact with the catalyst.These strategies usually also requires isolation of the degradation products in order to separate them from unwanted reagents such as solvents or catalysts.
The economic benefits of producing fuels from biomass depend for example on anefficient process for preparing the lignin and on the preparation of the lignin orlignin derivatives so that the fuel production is as efficient as possible. For examplethe amount oxygen should be as low as possible and the number of preparation steps should be as few as possible.SUMMARY OF THE INVENTION The object of the present invention is to overcome the drawbacks of the prior artand provide a composition comprising biomass of a high content and an organicsolvent, fatty acid or oil. The composition may comprise a carrier liquid such as afatty acid or an oil, with a high biomass material content such as lignin or ligninderivatives. In order to obtain a high biomass content the biomass have beenfunctionalized or modified by esterfication of the hydroxyl groups. One application for the composition may be as a raw material for fuel production.
The present invention facilitates the preparation of a composition suitable for fuelproduction which does not require pre-preparation steps such as degradation andisolation steps. Instead the functionalization of the biomass may be prepared in the carrier liquid in situ.
In a first aspect the present invention relates to a composition comprising a carrierliquid and hydroXyl group containing biomass, preferably lignin or ligninderivatives; Wherein the hydroxyl groups of the biomass have been substituted With ester groups of a fatty acid, preferably an unsaturated fatty acid.
In a second aspect the present invention relates to a method of preparing the composition according to the present invention comprising:a. Providing a carrier liquid, b. Providing biomass material containing hydroXyl groups preferably lignin or lignin derivatives; c. Providing an esterification reagent or, a fatty acid and an esterification reagent, and optionally a catalyst;d. Mixing the components of step b and c;e. Heating the mixture to at least 80°C; f. Letting the components react in order to obtain esterified biomass material;g. Optionally isolating the esterified biomass material; andh. Mixing the esterified biomass material With the carrier liquid.
In a third aspect the present invention relates to a product obtainable by the method of the present invention.
In a fourth aspect the present invention relates to the use of the method to prepare compositions for fuel production.
In a fifth aspect the present invention relates to a method of making fuel bythreating the composition according to the present invention in a hydro treater or a cat cracker.
In a sixth aspect the present invention relates to a fuel obtained from the composition according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION The present invention presents a composition for use in refinery processes for the production of various fuels.
In the present application the term “lignin derivative” means molecules or polymersderived from lignin. In the present application “lignin derivative” and “molecules orpolymers derived from lignin” are used interchangeably. These molecules orpolymers may be a result of chemical modification or degradation of lignin or alignin source, for example When treating black or red liquor in order to precipitate or separate lignin.
In the present application the term “carrier liquid” means a liquid selected fromorganic solvents, fatty acids or mixture of fatty acids, rosin acid, mineral oil and hydrocarbon oils or mixtures thereof.
In the present application the terms “red liquor” and “broWn liquor” denote the same liquor.
For a substance to be processed in a refinery such as an oil refinery or bio oilrefinery, the substance needs to be in liquid phase. Either the substance is in liquidphase at a given temperature (usually below 80 °C) or the substance is solvated in aliquid. In this patent application, such liquid Will be given the term carrier liquid.The present invention presents a composition and a method of preparing saidcomposition Where the composition comprises a biomass material, preferably ligninor lignin derivatives, Where the biomass material is in liquid phase and may beprocessed in a refinery. The present invention makes it easier or even facilitates production of fuel from biomass material.
Biomass includes, but is not limited to Wood, fruits, vegetables, processing Waste,chaff, grain, grasses, com, com husks, Weeds, aquatic plants, hay, paper, paperproducts, recycled paper, shell, broWn coal, algae, straW, bark or nut shells,lignocellulosic material, lignin and any cellulose containing biological material ormaterial of biological origin. In one embodiment the biomass is Wood, preferablyparticulate Wood such as saw dust or Wood chips. The Wood may be any kind ofWood, hard or soft Wood, coniferous tree or broad-leaf tree. A non-limiting list ofWoods Would be pine, birch, spruce, maple, ash, mountain ash, redWood, alder,elm, oak and beech.
Biornass niaterials and derivatives tiiereof often iiave a general formula of CXi-ïy-ÜZyiftiere tlne ratio z depends of ririgiri, paret of the plant' and also prortesses of tiiebitiniass material, and \w'he.re x and y each are al and. “Preferablgf is 22, orrnore preferablgf x is 23, or more preferalaljy' X is än; z is preferabljyf zl, or 22. ln oneernbodimeiit X is s 20, in another embodinient X is s 15, and in yet ariotiiereriibodimeiit x is :il i. ln one emiiodiinent z is 10 arid in anfitiier einbodinient z is . Tile hiornass rnateriai rnay comprise other iietíeroat-'onis silcli as S or 'Fhe following is a rion-limiting list of biomass materials: cellulose (C6H10O5)n,giuaïfise (CÖHQOÖ), glycerol (C3HSO3), ethanol (C2H6O); fatty acids such as,palmitoleic oil (C16H32O2), oleic acid (C18H34O2), tall oil or fatty acid C11H31.35COOH;rosin acids such as abeitic acid (C20H30O2); lignin or lignin derivatives in the rangebetween of Cl to C20, such as (C10H10O2), (C10H12O3), (C11H14O4), lignin in blackliquor such as (CmHgO), (C10H10O2), (C11H12O3) and pyrolysis oil, etc. The fatty acidssuch as palmitoleic oil (C16H32O2), oleic acid (C1gH34O2), tall oil or fatty acid C17H31_35COOH; rosin acids such as abeitic acid (C20H30O2); may also be used as acomponent in the composition according to the present invention. In oneembodiment the biomass material is lignin or lignin derivatives in the rangebetween of C1 to C20, such as (C9H10O2), (C10H12O3) and (C11H14O4) or lignin in orfrom black liquor such as (CgHgO), (C10H10O2) and (C11H12O3). Examples of ligninderivatives 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 oneembodiment the biomass material is black or red liquor, or materials obtained fromblack or red liquor. Black and red liquor contains cellulose, hemi cellulose andlignin and derivatives thereof. The composition according to the present inventionmay comprise black or red liquor, or lignin or lignin derivatives obtained from black or red liquor.
In another embodiment the biomass material comprises residual material fromethanol production such as cellulosic or corn ethanol production, hereafter calledethanol production. In another embodiment the biomass material is lignin or ligninderivatives obtained from ethanol production. In one embodiment the biomass material comprises hydroxyl groups.
Black liquor comprises four main groups of organic substances, around 30-45 Weight% ligneous material, 25-35 Weight% saccharine acids, about 10 Weight% formic and acetic acid, 3-5 Weight% extractives, about 1 Weight% methanol, andmany inorganic elements and sulphur. The exact composition of the liquor variesand depends on the Cooking conditions in the production process and thefeedstock. Red liquor comprises the ions from the sulfite process (calcium, sodium,magnesium or ammonium), sulfonated lignin, hemicellulose and low molecular resins.
The lignin may be kraft lignin, sulfonated lignin, Lignoboost® lignin, precipitatedlignin, filtrated lignin or 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 arthave presented various techniques to depolymerize and covert the depolymerized lignin into components soluble in the Wanted media.
When the biomass material comprises lignin or lignin derivatives the numberaverage molecular Weight (mass) (Mn) of the lignin may be 30,000 g/ mol or less,such as not more than 20,000 g/mol, or not more than 10,000 g/mol, or not morethan 5,000 g/mol, or not more than 2,000 g/mol, or not more than 1,000 g/mol. Inone embodiment the number average molecular Weight of the lignin is between 150and 4,000 g/mol, or between 300 and 1,000 g/mol.
The esterified lignin or lignin derivative may have a number average molecularWeight (Mn) of 300 g/mol or more, or 1,000 g/mol or more, or 5,000 g/mol or more, or 8,000 g/mol or more.
The composition may further comprise at least one additive. The additive may beany additive known to a person skilled in the art. In one embodiment the additivemay further enhance the dissolution of the lignin or lignin derivatives. The additivemay have the function of dissolving or breaking up inter molecular bonds betweenthe lignin chains or the lignin derivatives. In one embodiment the additive is a polar compound or a salt.
'The carrier liquid should preferab1y* be suitable for a hydro treater or a catalyticcracker (cat cracker), preferably a liquid suitable for both hydro treater andcatalytic cracker . Hydro treater and catalytic cracker are steps in the ref1neryprocess Where the sulfur content of the oil is reduced and Where high-boiling, high molecular Weight hydrocarbons are converted into gasoline, diesel and gases. In one embodiment the carrier liquid is a fatty acid or a mixture of fatty acids. In anotherembodiment the fatty acid or the mixture of the fatty acids comprises unsaturatedfatty acids, preferably at a concentration of more than 25 Wt%, or more than 50 Wt%. In one embodiment the carrier liquid is a tall oil. In another embodiment the carrier liquid is a hydrocarbon oil or a mineral oil.
When the carrier liquid is or comprises a hydrocarbon oil the oil needs to be inliquid phase below 80 °C and preferably have boiling points of 177-371 °C. Thesehydrocarbon oils include different types of or gas oils and likeWise e.g. Full RangeStraight Run Middle Distillates, Hydrotreated, Middle Distillate, Light CatalyticCracked Distillate, distillates Naphäïlna 'tilll-rarige st.1:":-1ighïi-r11r1, Dí-Ssaïçíllafaes,hydroaíesrlïfllrizeai. fïzíl-rzauuge, Išisïailíates, s<>1ve1:1t,-<1evvaxefí -fsaïçraiglxï-rzauuge,Distillates, straight-lfun :níddíeië suïfenjyflatení, Naphtha. c1ay-treat~<3§1 fuíl-lfangestraight min, Distilbates iïlíl-rzinrgz-:f atnï, Distíílatrâs hydrotreated ftilí-rfinge,Distillates, straight-mir: lígftït, Dístíllaiies heavy siír'aíg¿ht--r11:1, Dístiílaïies (oil 32111111),streaighíi--rurï :middle-fun, Plaphïha (särade oil), hgfdroatraatlied, iuíl--range streaigiïií :1111(example of but not restricted to CAS nr: 68476-30-2, 68814-87-9, 74742-46-7,64741-59-9, 64741-44-2, 64741-42-0, 101316-57-8, 101315-5183, 91721-'5-55-3,*Jïfiëšš-SS-íš, 68527429. 1-9, 1.".?.åšfí83-í26-1., §š1.§i°95~4í5-9, ö8410-05~Éï3, šíåšïäíš-Éšö-S,128683-27-2? 195459-1239). Moreover substances can be solvated in lighterhydrocarbon fractions such as organic solvents e.g. mesitylene, toluene, benzene,petroleum ether, octanes, nonanes, decanes and also isomerized derivatives of thesecompounds or mixtures thereof (CAS nr: 108-88-3, 108-67-8, 71-43-15, 8032-32-4,1111-65-19, 1.11-“"š4-2, 124-185).
The carrier liquid may also be an organic solvent, or a mixture of organic solvents,or a mixture of an organic solvent and a fatty acid and/ or an oil. The organicsolvent may but is not limited to oxygenates such as an alcohol, ester, ketone,ether, furane or furfural based solvent. Preferred solvents are Cl-C10 alcohols, C1-C1O ethers, and Cl-C10 esters, for example 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 tetrahydrofuran.Preferred Cl-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. In one embodiment the solvent comprises a combination of Cl-C10 alcohols, Cl-C10 ethers and Cl-C10 esters. In one embodiment the solventcomprises two Cl-C10 alcohols for example ethanol and glycerol, and in anotherembodiment the solvent comprises propanol and glycerol. In one embodiment thesolvent comprises polyethylene glycol and a Cl-C10 alcohol. In one embodiment thesolvent comprises furfural or furfuryl alcohol. When the solvent is a mixture of anorganic solvent and Water the mixture may contain methanol and Water, ethanoland Water, isopropanol and Water or ethyl acetate and Water, preferably ethanol and Water, isopropanol and Water and ethyl acetate and Water.
The composition according to the present invention may be prepared by firstpreparing the esterified biomass and then mixing said esterified biomass With thecarrier liquid. The esterified biomass may be isolated from the esterfication reactionmixture or the esterified biomass is left in the reaction mixture When mixed With thecarrier liquid. The esterfication of the biomass may also be performed in situ, i.e. inthe carrier liquid. Then the biomass, the esterfication agent or, the first fatty acidand an esterfication agent, and the carrier liquid and optionally a catalyst are mixedto form a slurry. The slurry is then preferably heated for example to 80°C or higher,or 120°C or higher. The esterfication of the biomass occurs in the carrier liquidleaving a homogenous composition of carrier liquid and esterified biomass, andoptionally catalyst. The catalyst and any other unWanted components may beremoved afterWards. The mixing can be done by stirring or shaking or in any othersuitable Way. When the esterfication is performed in a carrier liquid comprising afirst fatty acid and together With an esterfication agent such as an anhydride theobtained esterified lignin is believed to comprise ester groups derived from theanhydride 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 orWater. When the degree of substitution (esterfication) is high, for example 50% ormore, the esterified lignin may be treated With a base for example NaHCOS (aq)before precipitation. The esterified lignin according to the present invention mayalso be separated from metals and other additives or catalysts by simply rinsing thelignin in an aqueous solution or Water. For many industries, for example the fuelrefinery industry, processing lignin the amount of metals should be as low aspossible since metals may damage the machinery or disturb the process. Byforming the ester groups in situ insoluble biomass may become soluble. For example lignin substituted With acetic ester groups is not dissolved in tall oil.
However When forming the acetic ester in the tall oil the obtained homogenous mixture comprises 32 wt% of the formed lignin ester, see example 29.
The mixing may be performed at room temperature, but may be performed at atemperature between 50°C and 350°C, such as 50°C or higher, or 80°C or higher or100°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 esterfication agent may be a carboxylic acid or an anhydride. The esterficationagents preferably contain an unsaturated bond. Non-limiting examples of carboxylicacids are fatty acids or C2-C40 carboxylic esters, preferably C4 to C22. Non-limitingexamples of anhydrides are C4 to C42 anhydrides. The catalyst may be an imidazole or pyridine.
When the carrier liquid is a fatty acid (second fatty acid) said fatty acid may be butis not limited to C6-C18 fatty acids, saturated or unsaturated, or a mixtures of C2-C18 fatty acids. The fatty acid may further be methylated or ethylated. The secondfatty acid may be a vegetable fatty acid such as a tall oil, or olive oil, soybean oil,corn oil, hemp or coconut oil. In one embodiment the first and the second fatty acid are the same.
In one embodiment the carrier liquid is a second fatty acid or a mixture of secondfatty acids or a mixture comprising a second fatty acid. In one embodiment thesecond fatty acid is an unsaturated fatty acid or is a mixture of fatty acids in whichthe mixture contains unsaturated fatty acids. In one embodiment the first and the second fatty acids are the same, for example tall oils.
In one embodiment the composition comprises a first fatty acid or oil and lignin orlignin derivatives; wherein at least one of the hydroxyl groups of the lignin or ligninderivatives have been substituted with 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 beenconverted into ester groups, may be from 10% to 100%, for example 20% or more, or 40% or more, or 60% or more or 80% or more.
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 11 substituted With a saturated ester group is a solid or Wax like material. By havingthe lignin in oil phase there is no need to heat the lignin in order for it to dissolve inthe Wanted solvent. In order to keep the Wax like lignin in solution it needs to bekept at the elevated temperature (for example 70°C) Which makes transportationand stock keeping more costly. This issue is solved With the present invention and instead the composition may be prepared at room temperature.
Substituting the hydroxyl groups of the lignin increases the solubility in organicsolvents. The inventors found that even at low degree of substitution (O.3equivalents, 60% degree of substitution) the lignin becomes soluble in ethyl acetate,methyl THF, cyclopentyl methyl ether and iso-propanol. This is especiallypronounced When the ester group is a C6 or longer chain, preferably C14 or longer chain.
When the method of the present invention is performed using black or red liquorthe liquor may be pre-treated by evaporation, separation or filtration or via chemicaltreatments such as the process described below and further defined in WO2012/ 121659.
The biomass material in the composition may have been treated With the processdescribed in WO2012/ 121659 Which is hereby incorporated by reference. Theprocess relates to reduction of a substrate Wherein said substrate can be but is notlimited to primary, secondary and tertiary benzylic or allylic alcohol, benzylic orallylic ether, benzylic or allylic carbonyl, and benzylic or allylic ester, or olefins tothe corresponding hydrocarbon. The substrate may be lignin or any othercompound or polymer comprising said functional group, or black or red liquor. Ageneral method comprises adding a catalyst, a transition metal catalyst, to areaction flask or container. Adding a solvent mixture of at least two solvents Whereone of the solvents is Water and a base. The mixture is then heated followed byaddition of a hydrogen donor and the substrate to be reduced. In order to inhibitdisproportionation, a base or carbon dioxide should be added to the solvent mixtureand catalyst prior to addition of a hydrogen donor and the substrate. The hydrogendonor 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 theamount of base is not stoichiometric to the amount of the substrate. The biomassmaterial or preferably the separated lignin and lignin derivatives obtained from the reduction method may then be used as the biomass material in the composition 12 according to the present invention. In one embodiment the obtained biomassmaterial from the chemical reduction is further treated With filtration, ultra-filtration or cross-flow ultra-filtration; or treated With acidification and separation such as the Lignoboost® technique.
In another embodiment the composition of the present invention may comprise abiomass material comprising lignin or lignin derivatives obtained throughprecipitation and separation of lignin and lignin derivatives for example byacidification and separation, such as f1ltration. Lignoboost® or any other similarseparation technique are examples of such technique and may be used. Theseparated lignin and lignin derivatives may then be used as the biomass material inthe composition according to the present invention. In another embodiment theseparated 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 specificcomponents in a biomass material is through filtration, ultra-filtration or cross-flowultra-filtration. When the biomass material comprises lignin or lignin derivatives,the lignin may be separated in respect to size through any of said f1ltrationtechniques. The lignin or lignin derivatives may also be separated in respect to sizethrough a depolymerisation technique; this separation may be performed incombination With filtration, ultra-filtration or cross-flow ultra-filtration. By usingfiltration, ultra-filtration or cross-flow ultra-filtration on black or red liquor lignin orlignin 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 of2,000g/mol or less, such as 1,000 g/mol or less. The separated lignin and ligninderivatives may then be used as the biomass material in the composition accordingto the present invention. In one embodiment the lignin and lignin derivativesobtained from said f1ltration may further be chemically reduced using the methoddescribed above and in WO2012/ 121659.
The composition according to the present invention may be used in a refineryprocess 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.
The composition according to the present invention may also be used as anadditive, for example as a concreted grinding aid, set retarder for cement, strengthener of cement, antioxidant, enhancer of thermal protection, stabilizer in 13 asphalt, emulsifying agent, fiber strengthening additive, cross-linking agent, boardbinder, anti-corrosion additive, wear resistant additive, antifriction additive, binder, emulsif1er 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 waterabsorption inhibitor or as a fluidization agent. Mechanical properties may also be enhanced by the use of the composition.
The composition may be added to surfaces to obtain dust control, or the composition may be used to prepare batteries.
EXAMPLES In some of the examples below the following lignin types have been used.
Lignin type A1: acid precipitated lignin from black liquor Lignin type A2: acid precipitated lignin from black liquor dried to 95 % dry weight Lignin type A3: hexyl ester of acid precipitated lignin from black liquor Lignin type B: f1ltrated black liquor Lignin type C: lignin depolymerized using the method according to WO2012/ 121659 In the examples below the symbol “<” means that not all of the substrate for example lignin was dissolved.
Example 1 To a solution of ethyl acetate (0. 1044 g) Lignin type A2-Ac-ester (0. 1046 g) wasadded. The suspension was stirred under heating (70 °C). A pourable solution at 70°C comprising 50 weight% of Lignin type A2-Ac-ester was attained.
Example 2 To a solution of ethanol (0.0858 g) Lignin type A2-Ac-ester (0.1086 g) was added.The suspension was stirred under heating (70 °C). A pourable solution at 70 °C comprising 56 weight% of Lignin type A2-Ac-ester was attained. 14 Example 3 To a solution of acetone (0.0592 g) Lignin type A2-Ac-ester (0. 1012 g) Was added.The suspension Was stirred under heating (70 °C). A pourab1e solution at 70 °C comprising 63 Weight% of Lignin type A2-Ac-ester Was attained.Example 4 To a so1ution of po1yethy1ene g1yco1 (0. 1372 g) Lignin type A2-Ac-ester (0.0986 g)Was added. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70 °C comprising 42 Weight% of Lignin type A2-Ac-ester Was attained.Example 5 To a so1ution of g1ycero1 (1.1634 g) Lignin type A2-Ac-ester (0.1032 g) Was added.The suspension Was stirred under heating (70 °C). A so1ution comprising < 8 Weight% of Lignin type A2-Ac-ester Was attained.Example 6 To a so1ution of 2-methy1tetrahydrofuran (0.0865 g) Lignin type A2-Ac-ester (0.0981g) Was added. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70 °C comprising 53 Weight% of Lignin type A2-Ac-ester Was attained.Example 7 To a so1ution of cyc1openty1 methyl ether (0.7775 g) Lignin type A2-Ac-ester (0. 1027g) Was added. The suspension Was stirred under heating (70 °C). A so1ution comprising < 12 Weight% of Lignin type A2-Ac-ester Was attained.Example 8 To a so1ution of 1,3-propanedio1 (1.5005 g) Lignin type A2-Ac-ester (0. 1063 g) Wasadded. The suspension Was stirred under heating (70 °C). A so1ution comprising < 7 Weight% of Lignin type A2-Ac-ester Was attained.Example 9 To a so1ution of 1,3-dioxolane (0.0905 g) Lignin type A2-Ac-ester (0. 1043 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 54 Weight% of Lignin type A2-Ac-ester Was attained.
Example 10 To a solution of dipropy1ene g1yco1 (0.1142 g) Lignin type A2-Ac-ester (0. 1038 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e solution at 70°C comprising 48 Weight% of Lignin type A2-Ac-ester Was attained.
Example 1 1 To a so1ution of dipropy1ene g1yco1 (0.1631 g) Lignin type A2-Ac-ester (0.1057 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 39 Weight% of Lignin type A2-Ac-ester Was attained.
Example 12 To a so1ution of 1,4-dioxane (0.0772 g) Lignin type A2-Ac-ester (0.0987 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 56 Weight% of Lignin type A2-Ac-ester Was attained.
Example 13 To a so1ution of methano1 (0.0693 g) Lignin type A2-Ac-ester (0.0986 g) Was added.The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70 °C comprising 59 Weight% of Lignin type A2-Ac-ester Was attained.Example 14 To a so1ution of isopropano1 (0.9031 g) Lignin type A2-Ac-ester (0. 1064 g) Wasadded. The suspension Was stirred under heating (70 °C). A so1ution comprising < 1 1 Weight% of Lignin type A2-Ac-ester Was attained.Example 15 To a so1ution of dimethy1su1foxide (0.0995 g) Lignin type A2-Ac-ester (0. 1034 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 51 Weight% of Lignin type A2-Ac-ester Was attained.
Example 16 To a so1ution of tetrahydrofuran (0.0856 g) Lignin type A2-Ac-ester (0. 1063 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 55 Weight% of Lignin type A2-Ac-ester Was attained. 16 Example 17 To a solution of pyridine (0. 1008 g) Lignin type A2-Ac-ester (0. 1080 g) Was added.The suspension Was stirred under heating (70 °C). A pourab1e solution at 70 °C comprising 52 Weight% of Lignin type A2-Ac-ester Was attained.Example 18 To a so1ution of acetic acid (0.0887 g) Lignin type A2-Ac-ester (0.0986 g) Was added.The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70 °C comprising 53 Weight% of Lignin type A2-Ac-ester Was attained.Example 19 To a so1ution of hexanoic acid (1. 1881 g) Lignin type A2-Ac-ester (0. 1080 g) Wasadded. The suspension Was stirred under heating (70 °C). A so1ution comprising < 8 Weight% of Lignin type A2-Ac-ester Was attained.Example 20 To a so1ution of isophorone (0.0835 g) Lignin type A2-Ac-ester (0. 1021 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 55 Weight% of Lignin type A2-Ac-ester Was attained.
Example 21 To a so1ution of mesity1 oxide (0.0670 g) Lignin type A2-Ac-ester (0. 1025 g) Wasadded. The suspension Was stirred under heating (70 °C). A pourab1e so1ution at 70°C comprising 60 Weight% of Lignin type A2-Ac-ester Was attained.
Example 22 To a via1 containing Lignin type A2 (0.2079 g) l-methylimidazole (0.020 g), aceticanhydride (0.2046 g), and a mixture comprising free fatty acids (0.2977 g) Wasadded. The suspension Was stirred under heating (100 °C, 24 h). A pourab1eso1ution at 70 °C comprising 28 Weight% of Lignin type A2 Was attained.
Example 23 To a via1 containing Lignin type A2 (0. 1932 g) l-methylimidazole (0.020 g), aceticanhydride (0.2028 g), and a mixture comprising free fatty acids (0.4341 g) Was 17 added. The suspension Was stirred under heating (100 °C, 24 h). A pourab1esolution at 70 °C comprising 23 Weight% of Lignin type A2 Was attained.
Example 24 To a suspension comprising free fatty acids and type Lignin type C 1ignin (0.1084 g)acetic anhydride as Well as l-methylimidazole (2 drp) Was added. The suspensionWas stirred under heating (70 °C, 1 h). A so1ution comprising type Lignin type C 1ignin Was attained.
Example 25 To a suspension of gas oi1 and type Lignin type C 1ignin (0.0995 g) acetic anhydride,a miXture comprising free fatty acids as Well as l-methylimidazole (2 drp) Wasadded. The suspension Was stirred under heating (70 °C, 1 h). A so1ution comprising type Lignin type C 1ignin Was attained.
Example 26 To a so1ution of gas oi1 (0.0584 g) Lignin type A2-Myr-ester (0.0195 g) (Myr is a C14fatty acid) Was added. The suspension Was stirred under heating (70 °C). A pourab1eso1ution at 70 °C comprising 25 Weight% of Lignin type A2-Myr-ester Was attained.
Example 27 To a so1ution of hexanoic anhydride (0.9108 g) and l-methylimidazole (0.0160 g)Lignin type A1 (0.407 g) Was added. The suspension Was stirred under heating (120°C) for 2h forming an esterified 1ignin. Upon Cooling a so1ution comprising 30.9Weight% of Lignin type A1 Was attained. The so1ution Was then disso1ved in amiXture of fatty acid derived from biomass in a 1:1 ratio yie1ding a so1ution comprising 15 Weight% of Lignin type A1.
Example 28 To a so1ution of hexanoic anhydride (0.4 g) and a miXture comprising fatty acids(0.4 g) derived from biomass, Lignin type A2 (0.4 g) Was added, as Well as two dropsof l-methylimidazole. The suspension Was stirred under heating (120°C) for 2hforming an esterified 1ignin. A pourab1e so1ution at 70 °C comprising 33 Weight% of Lignin type A2 Was attained. 18 Example 29 To a solution of acetic anhydride (0.2060 g) and a mixture comprising fatty acids(0.2278 g) derived from biomass, the Lignin type A2 (0.2034 g) Was added, as Wellas two drops of 1-methylimidazole. The suspension Was stirred under heating(100°C) for 24h. A pourab1e so1ution at 70 °C comprising 32 Weight% of Lignin type A2 Was attained.Example 30 To a so1ution of hexanoic anhydride (0.2040 g) and a mixture comprising fatty acids(0.2189 g) derived from biomass, Lignin type A2 (0.2007 g) Was added, as Well astwo drops of l-methylimidazole. The suspension Was stirred under heating (100°C)for 24h. A pourab1e so1ution at 70 °C comprising 32 Weight% of Lignin type A2 Was attained.Example 31 To a so1ution of ethy1 acetate (0.1398 g) Lignin type A3 (0.0961 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 41 Weight% of Lignin type A3 Was attained.Example 32 To a so1ution of acetone (0.0885 g) Lignin type A3 (0. 1038 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 54 Weight% of Lignin type A3 Was attained.Example 33 To a so1ution of po1yethy1ene g1yco1 (1.3309 g) Lignin type A3 (0. 1021 g) Was added.The suspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising < 7 Weight% of Lignin type A3 Was attained.Example 34 To a so1ution of 2-methy1tetrahydrofuran (0. 1085 g) Lignin type A3 (0. 1013 g) Wasadded. The suspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 48 Weight% of Lignin type A3 Was attained. 19 Example 34 To a solution of cyc1openty1 methylether (0.1 124 g) Lignin type A3 (0.0996 g) Wasadded. The suspension Was stirred under heating. A pourab1e solution at 70 °C comprising 47 Weight% of Lignin type A3 Was attained.Example 35 To a so1ution of 1,3-dioxo1ane (0.0967 g) Lignin type A3 (0. 1006 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 51 Weight% of Lignin type A3 Was attained.Example 36 To a so1ution of furfura1 (0.1727 g) Lignin type A3 (0. 1040 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 38 Weight% of Lignin type A3 Was attained.Example 37 To a so1ution of dipropy1ene g1yco1 (0.2092 g) Lignin type A3 (0. 1032 g) Was added.The suspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 33 Weight% of Lignin type A3 Was attained.Example 38 To a so1ution of 1,4-dioxane (0. 1260 g) Lignin type A3 (0.0969 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 43 Weight% of Lignin type A3 Was attained.Example 39 To a so1ution of methanol (0. 1022 g) Lignin type A3 (0. 1044 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 51 Weight% of Lignin type A3 Was attained.Example 40 To a so1ution of isopropano1 (0.0775 g) Lignin type A3 (0.0955 g) Was added. Thesuspension Was stirred under heating. A pourab1e so1ution at 70 °C comprising 55 Weight% of Lignin type A3 Was attained.
Example 41 To a solution of dimethyl sulfoxide (0.2907 g) Lignin type A3 (0. 1037 g) Was added.The suspension Was stirred under heating. A pourable solution at 70 °C comprising 26 Weight% of Lignin type A3 Was attained.Example 42 To a solution of tetrahydrofuran (0. 1065 g) Lignin type A3 (0.0974 g) Was added.The suspension Was stirred under heating. A pourable solution at 70 °C comprising 48 Weight% of Lignin type A3 Was attained.Example 43 To a solution of pyridine (0.1183 g) Lignin type A3 (0.0993 g) Was added. Thesuspension Was stirred under heating. A pourable solution at 70 °C comprising 46 Weight% of Lignin type A3 Was attained.Example 44 To a solution of acetic acid (0. 1460 g) Lignin type A3 (0. 1014 g) Was added. Thesuspension Was stirred under heating. A pourable solution at 70 °C comprising 41 Weight% of Lignin type A3 Was attained.Example 45 To a solution of hexanoic acid (0. 1527 g) Lignin type A3 (0. 1040 g) Was added. Thesuspension Was stirred under heating. A pourable solution at 70 °C comprising 41 Weight% of Lignin type A3 Was attained.Example 46 To a miXture (0.2077 g) mainly comprising fatty acid derived from biomass, Lignintype A3 (0.0927 g) Was added. The suspension Was stirred under heating. Apourable solution at 70 °C comprising 31 Weight% of Lignin type A3 Was attained.
Example 47 Anhydride of tall oil fatty acids. 21 To tall oil fatty acids (10.00 g, 1 eq) in dichloromethane (20 ml) was addeddicyclohexylcarbodiimide (4.13 g, ca 0.5 eq) in one portion. The reaction was stirredunder argon at room temperature for 6 h, followed by addition of pentane (20 ml),filtering and washing the solids with pentane (15 ml). The clear liquids werecombined and solvent was evaporated to give 10.66 g of crude anhydride of tall oil fatty acids as thick slightly yellow oil.Example 48Acetic acid ester.
To a stirred suspension of Lignin type A2 (5.00 g) and acetic anhydride (50 ml)pyridine (50 ml) was added in two portions. The atmosphere was replaced by argonand stirring was continued overnight at room temperature. Solution was cooled inice bath and cold methanol (150 ml) was added. After evaporating the solvent, theresidue was co-evaporated several times with toluene until solid material wasobtained. The residue was dissolved in dichloromethane and precipitated withheptane. The clear solution was decanted, the solids were powdered and driedthoroughly in a desiccator under high vacuum over KOH to give 6.89 g of the acetyl ester as brown powder.Example 49Lauric acid ester.
Lignin type A2 (1.00 g, 1 equivalent), lauric anhydride (4.25 g, 2 eq) and dioXane (10ml) were stirred under argon and l-methylimidazole (0.1 ml) was added. Thereaction was continued at 80 °C overnight. After cooling to room temperature theliquid was poured into vigorously stirred water (130 ml). The liquid was decantedand the residue was redissolved in tetrahydrofuran and the product wasprecipitated with water. The decantation and the precipitation were repeated oncemore. The crude product was dried, redissolved in chloroform and adsorbed oncelite (32 g). After thorough drying the solids were stirred with aqueous 0.5 Msolution of NaHCOg, (400 ml) overnight under argon. This treatment transformedfree carboxylic acid to its corresponding sodium salt having higher aff1nity to celitethan lignin ester. In some cases it was required to add tetrahydrofuran until solids were wetted to ensure faster neutralisation of the free acid. 22 The celite With adsorbed product was filtered, washed With water and dried undervacuum. The ester was washed off with hexane to give 1.32 g of the lauric acid ester as brown residue after evaporation of the solvent.Example 50Caproic acid ester.
According to the general procedure of esterification, with modifications, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), caproic anhydride (12.8 ml, 2 eq),l-methylimidazole (0.44 ml, 0.2 eq) and dioxane (30 ml). A part of the product wasprecipitated by pouring into hexane (500 ml) under sonication. The solids werefiltered, redissolved in dioXane (10 ml) and poured into hexane (200 ml). Theprecipitation was repeated once more to give 4.41 g of hexanoic anhydride ester as yellowish powder.
The dark brown supernatants after precipitation were combined, suspended withcelite (100 g) and solvent was evaporated thoroughly. To the obtained powder wasadded aqueous 0.5 M solution of NaHCOg, (800 ml) and the resulting suspensionwas stirred under argon overnight. After filtering the solids, washing with water anddrying under vacuum the remaining ester was washed off withtetrahydrofuran:hexane 1:1 to give 3.26 g of brown residue after evaporation of thesolvents. This product was combined with the ester isolated after hexaneprecipitation, dissolved in 20 ml dioXane and freeze dried to give 7.24 g of heXanoic acid ester as light brown sponge.Example 51Cis-3-hexenoic acid ester.
Same procedure as for caproic acid ester, except that following amounts were used:Lignin type A2 (1.00 g, 1 eq), cis-3-hexenoic acid anhydride (2.34 g, 2 eq), 1-methylimidazole (0.1 ml) and dioxane (10 ml). The precipitation afforded 1.22 g ofthe ester. Subsequent purif1cation of the precipitation supernatants by celite (20 g)and a solution of NaHCOg, (200 ml) as described in caproic acid ester synthesisafforded 0.2 g of brown residue. Combination of these two fractions of products andfreeze drying from 10 ml dioxane afforded 1.4 g of cis-3-heXanoic acid ester as brown solid. 23 Example 52 Myristic acid esters.
Partial substitutions: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), myristic anhydride (0.24 or 0.73g, 0.1 or 0.3 eq), 1-methylimidazole (0.1 ml) and dioXane (5 ml). After the reaction the esters were purified according to procedures below.
Example 53 Purification procedure of partially substituted esters: 0.1-eq reaction was poured into hexane (50 ml) under sonication. After filtering, thesolids were redissolved in dioxane (5 ml) and precipitation was repeated once moreto give 1.12 g of the ester as brown powder. 0.3-eq reaction was worked up in thesame way to give 1.23 g of the ester as brown powder. Generally 1-3 precipitationswere sufficient for all partially substituted esters to give a product free from thecarboxylic acid. The presence of free carboxylic acid was monitored using TLC on silica-coated plates using hexane:ethyl acetate:acetic acid as the eluent.
In some cases centrifuge was used to separate solid product.
Example 54 Stearic acid esters.
Full substitution: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), stearic anhydride (6.12 g, 2 eq),l-methylimidazole (0.1 ml) and dioxane (15 ml). For purification, celite (50 g) wasused with 0.5 M solution of NaHCOg (400 ml). Some tetrahydrofuran was added towet the celite. The ester was washed off with neat hexane to give 1.97 g of stearic acid ester as a brown solid.
Partial substitutions: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), stearic anhydride (0.31 or 0.92 g,0.1 or 0.3 eq), 1-methylimidazole (0.1 ml) and dioxane (10 ml). After the reaction theesters were purified according to the general purification of partially substitutedesters. 0.1 and 0.3-eq reactions afforded 1.12 g and 1.01 g respectively of the corresponding esters as brown powders. 24 Example 55 Oleic acid esters.
Full substitution: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), oleic anhydride (6.08 g, 2 eq), 1- methylimidazole (0.1 ml) and dioxane (10 ml).
The product was purified by dissolving in chloroform and washing with waterfollowed by celite purification. For further purification celite (50 g) was used with0.5 M solution of NaHCOg, (400 ml). The ester was washed off with neat hexane to give 2.49 g of oleic acid ester as brown thick oil.
Partial substitutions: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), oleic anhydride (0.30 or 0.91 g,0.1 or 0.3 eq), 1-methylimidazole (0.1 ml) and dioxane (10 ml). After the reaction theesters were purified according to the general purification of partially substitutedesters. 0.1 and 0.3-eq reactions afforded 1.13 g and 1.18 g respectively of the corresponding esters as brown powders.
Example 56 Behenic acid esters.
Full substitution: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), behenic anhydride (7.37 g, 2 eq),l-methylimidazole (0.1 ml) and dioxane (20 ml). The product was purified bydissolving in chloroform and washing with water followed by celite purification. Forfurther purification, celite (50 g) was used with 0.5 M solution of NaHCOg, (400 ml).Some tetrahydrofuran was added to wet the celite. The ester was washed off with hexane:tetrahydrofuran 1:1 to give 2.62 g of behenic acid ester as a brown solid.
Partial substitutions: According to the general procedure of esterification, followingamounts were used: Lignin (1.00 g, 1 eq), behenic anhydride (0.37 or 1.11 g, 0.1 or0.3 eq), l-methylimidazole (0.1 ml) and dioxane (10 ml). After the reaction the esterswere purified according to the general purification of partially substituted esters. 0.1 and 0.3-eq reactions afforded 1.15 g and 1.20 g respectively of the corresponding esters as brown powders.
Example 57 Erucic acid esters.
Full substitution: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), erucic anhydride (5.49 g, 1.5 eq),l-methylimidazole (0.1 ml) and dioxane (15 ml). The product was purified bydissolving in chloroform and washing with water, followed by celite purification. Forfurther purification, celite (50 g) was used with 0.5 M solution of NaHCOg, (400 ml).Some tetrahydrofuran was added to wet the celite. The ester was washed off with hexane to give 2.57 g of erucic acid ester as brown thick oil.
Partial substitutions: According to the general procedure of esterification, followingamounts were used: Lignin type A2 (1.00 g, 1 eq), erucic anhydride (0.37 or 1.10 g,0.1 or 0.3 eq), 1-methylimidazole (0.1 ml) and dioxane (10 ml). After the reaction theesters were purified according to the general purification of partially substitutedesters. 0.1 and 0.3-eq reactions afforded 1.13 g and 1.17 g respectively of the corresponding esters as brown powders.
Example 58 Tall oil fatty acid ester.
According to the general procedure of esterification, following amounts were used:Lignin type A2 (1.00 g, 1 eq), anhydride of tall oil fatty acids (5.36 g, ca 2 eq), 1-methylimidazole (0.1 ml) and dioXane (10 ml). Product was purified by dissolving inchloroform and washing with water. For further purification, celite (50 g) was usedwith 0.5 M solution of NaHCOg, (400 ml). The ester was washed off with heXane togive 3.91 g of tall oil fatty acid ester as brown thick oil.

Claims (15)

. A composition comprising a first fatty acid or oil and lignin or lignin derivatives; Wherein at least one of the hydroxyl groups of the lignin or ligninderivatives have been substituted With ester groups of a second fatty acid forming esterified lignin or lignin derivatives.
1. . The composition according to claim 1 Wherein the concentration of the esterified lignin or lignin derivatives in the composition is at least 10 Wt%, preferably at least 20 Wt%, or preferably at least 30 Wt%.
2. . The composition according to any one of claim 1 or 2 Wherein the hydroXyl groups of the lignin has been substituted to a degree of substitution of at least 20%, preferably at least 60%.
3. . The composition according to any one of the preceding claims Wherein the lignin or lignin derivative has a Weight average molecular Weight of not more than 2,000g/mol.
4. . The composition according to any one of the preceding claims Wherein the first fatty acid and the second fatty acid are the same.
5. . The composition according to any one of the preceding claims Wherein the second fatty acid is unsaturated, for example a tall oil.
6. . A method of preparing the composition according to any one of claims 1 to 6
7. Wherein the method comprises the stepsa. Providing a first fatty acid or an oil, and lignin or lignin derivatives; b. Providing an esterification reagent or, a second fatty acid and an esterification reagent, and optionally a catalyst;c. Mixing the components of step a and b to form a slurry;d. Heating the mixture; and e. Letting the components react in order to form a homogenouscomposition of esterified lignin or lignin derivatives in a first fatty acid or oil. 27
8. The method according to claim 7 Wherein esterification reagent is an anhydride or a furfuryl.
9. The method according to any one of claims 8 or 9 Wherein an imidazole or an acid is added as a catalyst.
10.The method according to any one of claims 8 to 10 Wherein the mixture is heated to at least 80°C, or preferably at least 120°C.
11.The use of the method according to any one of claims 8 to 11 to prepare compositions for fuel production.
12.A composition obtainable by the method according to any one of claims 8 to1 1.
13. 13. Use of the method according to any one of claims 7 to 10 to prepare compositions for fuel production.
14. A method for making fuel by treating the composition according to any one of claims 1 to 6 in a hydro treater or a catalytic cracker.
15. A fuel obtained from the composition according to any one of claims 1 to 6.
SE1351508A 2013-12-16 2013-12-16 Composition comprising fatty acids and esters of lignin SE537732C2 (en)

Priority Applications (26)

Application Number Priority Date Filing Date Title
SE1351508A SE537732C2 (en) 2013-12-16 2013-12-16 Composition comprising fatty acids and esters of lignin
PL14870806T PL3083652T3 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
PCT/SE2014/051507 WO2015094099A1 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
DK14870806.8T DK3083652T3 (en) 2013-12-16 2014-12-16 COMPOSITION INCLUDING ESTERS OF LIGNIN AND OIL OR FATTY ACIDS
CN201480074489.5A CN106132976B (en) 2013-12-16 2014-12-16 Composition comprising lignin ester and oil or fatty acid
US15/104,702 US10030147B2 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
EP21182866.0A EP3910029A1 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
BR112016013916-0A BR112016013916B1 (en) 2013-12-16 2014-12-16 composition comprising a liquid vehicle and lignin or lignin derivatives solubilized in said liquid carrier, method for producing fuels by treating the composition, fuel or lubricant and method for preparing the composition
SG11201604775TA SG11201604775TA (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
EP14870806.8A EP3083652B1 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
CA2933848A CA2933848C (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
US15/104,664 US20160312029A1 (en) 2013-12-16 2014-12-16 Composition Comprising Esters Of Lignin And Organic Solvent
EP14872144.2A EP3083653A4 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and organic solvent
RU2016125714A RU2690503C1 (en) 2013-12-16 2014-12-16 Composition containing lignin esters and oil or fatty acids
CN201480074490.8A CN106164084A (en) 2013-12-16 2014-12-16 Comprise the compositions of lignin ester and organic solvent
CA2933841A CA2933841A1 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and organic solvent
PCT/SE2014/051506 WO2015094098A1 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and organic solvent
PT14870806T PT3083652T (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
BR112016013905A BR112016013905A2 (en) 2013-12-16 2014-12-16 COMPOSITION COMPRISING AN ORGANIC SOLVENT AND LIGNIN OR LIGNIN DERIVATIVES, METHOD FOR PRODUCING FUELS BY TREATMENT OF THE COMPOSITION, FUEL, LUBRICANT, AND METHOD FOR PREPARING THE COMPOSITION
JP2016559143A JP6525343B2 (en) 2013-12-16 2014-12-16 Composition comprising an ester of lignin and an oil or fatty acid
ES14870806T ES2895101T3 (en) 2013-12-16 2014-12-16 Composition comprising esters of lignin and oil or fatty acids
JP2016559142A JP2017501290A (en) 2013-12-16 2014-12-16 A composition comprising an ester of lignin and an organic solvent
CN201910052890.3A CN110079365B (en) 2013-12-16 2014-12-16 Compositions comprising lignin esters and oils or fatty acids
CL2016001542A CL2016001542A1 (en) 2013-12-16 2016-06-16 Composition comprising esters of lignin and oil or fatty acids, useful for preparing fuels or lubricants.
US16/014,271 US10421861B2 (en) 2013-12-16 2018-06-21 Composition comprising esters of lignin and oil or fatty acids
US16/540,111 US10781313B2 (en) 2013-12-16 2019-08-14 Composition comprising esters of lignin and oil or fatty acids

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10676688B2 (en) 2015-06-15 2020-06-09 Ren Fuel K2B Ab Composition comprising derivatized lignin for fuel production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10676688B2 (en) 2015-06-15 2020-06-09 Ren Fuel K2B Ab Composition comprising derivatized lignin for fuel production

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