SE1551569A1

SE1551569A1 - Depolymerized lignin in hydrocarbon oil

Info

Publication number: SE1551569A1
Application number: SE1551569A
Authority: SE
Inventors: Orebom Alexander
Original assignee: Ren Fuel K2B Ab
Priority date: 2015-12-01
Filing date: 2015-12-01
Publication date: 2017-06-02
Also published as: SE542463C2; WO2017095316A1

Abstract

The present invention relates to a composition comprising lignin derivative and a solvent; wherein the lignin derivative has a weight average molecular weight (M) of 250g/mol to 650g/mol.

Description

TITLEDEPOLYMERIZED LIGNIN IN HYDROCARBON OIL FIELD OF THE INVENTION The present invention relates to a composition of lignin derivative and a solventsuch as a hydrocarbon oil, fatty acid or the like. The composition may be used as an additive to fuels but it is also suitable for refinery process for preparing 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, corn, corn 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 liquid fuels.

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. furtherfunctionalization. Lignin is known to have a low ability to sorb water compared to for example the hydrophilic cellulose. 2 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. Ligniii liststiigher energy' content; than cellufupse or txern.if:ell'tf.lï>ses sind one grarn of lígrlít: hasor1 average 2.237 KJ, væfhif;l*ï LÉ-fFÉ/š» more tlxan the erlergy' cfmtenií of ce1h;:.l<'>sí<ïastrbohydraïçe. mxergy' content oifíignín is sirnííar to tlfiat of fjcæﬁl. 'ï'od:ﬁ§/, due toits fuel value lignin that 11:15 been rerncvae-:í using the kraft process, sulphateprocess, in a 'gßulgja for pagæer ïníll, usually latiriïed ir; order' to prïz-*Jícle energy" to run tlïxf: production 'process and to reoovex' tlïxe cherníatæils frat-m the cooliíng licíuor.

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 membrane orultra-filtration. Lignoboost® is a separation process developed by Innventia AB andthe process has been shown to increase the lignin yield using less sulphuric acid. Inthe Lignoboost® process, black liquor from the production processes is taken andthe lignin is precipitated through the addition and reaction With acid, usuallycarbon dioXide (C02), and the lignin is then filtered off. The lignin filter cake is thenre-dispersed and acidif1ed, 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 forfuel production is the issue of providing lignin in a form suitable for hydrotreatersor crackers. The problem is that lignin is not soluble in oils or fatty acids Which is, if not necessary, highly Wanted. 3 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.WO2008/ 157164 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.

In WO2015/ 094099 the present applicant presents a strategy where lignin ismodified with an alkyl group via an ester linkage in order to make the lignin moresoluble in oils or fatty acids. In WO2014/ 1 16173 the present applicant teaches acomposition of lignin or lignin derivatives in a carrier liquid and a solvent where the lignin has a molecular weight of not more than 5,000g/mol.

WO2014/ 193289 teaches a method where black liquor is membrane filtratedfollowed by a depolymerization step where after the depolymerized lignin isseparated. The depolymerization may be done by treating the membrane filtrated lignin at high temperature and pressure.

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 of oxygen should be as low as possible and the number of preparationsteps should be as few as possible. A high oxygen content requires more hydrogen during the refinery process.

One way of making fuel production of lignin more beneficial would be if lignin maybe processed using common oil refinery techniques such catalytic cracking orhydrotreatment. In order to do that the lignin needs to be soluble in refinery media such as hydrocarbon oils.

SUMMARY OF THE INVENTION The object of the present invention is to overcome the draWbacks of the prior artand provide a composition comprising lignin derivative and a solvent. The ligninderivative is not only depolymerized it is also deoxygenated fully or partially, i.e. theoxygen content is reduced. One application for the composition may be as a raw material for fuel production or as an additive to fuel or oil.

In a first aspect the present invention relates to a composition comprising ligninderivate and a solvent liquid Wherein the lignin derivative has a Weight average molecular Weight of 250-650g/ mol.

In a second aspect the present invention relates to a method of preparing the composition according to the present invention comprising-adding an alkali aqueous lignin solution to a container;-sealing the container; -heating the black or red liquor to at least 270°C to depolymerize the lignin to amolecular Weight of 250-650g/mol; and -miXing the depolymerized lignin With a solvent.

In a third aspect the present invention relates to a method of preparing fuelcomprising treating the composition according to the present invention in a hydrotreater or a catalytic cracker.

In a fourth aspect the present invention relates to a fuel obtained from the composition according to the present invention.

In a fifth aspect the present invention relates to a fuel additive comprising the composition according to the present invention.

In a sixth aspect the present invention relates to a fuel comprising the composition according to the present invention.

In a seventh aspect the present composition may be used as a concreted grindingaid, 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 resistantadditive, antifriction additive, binder, emulsif1er or dispersing agent, cross-linkingor curing agent, or as a Water absorption inhibitor or as a ﬂuidization agent, as ananti-bacterial or anti-fungal surface or as a barrier, to impregnate Wood or as an anti-corrosion agent.

In an eight aspect the present invention may be used for producing tyres or paint.

BRIEF DESCRIPTION OF FIGURES Figure 1, schematic view of lignin.

Figure 2, table over yield and coke formation from the method according to the present invention.

Figure 3, char formation from the present invention and the effect of alcohol addition to the method.

Figure 4, graph disclosing the effect of lignin concentration and char formation.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for use in a refinery processes for the production of various fuels or chemicals.

In the present application the term “lignin” means a polymer comprising coumarylalcohol, coniferyl alcohol and sinapyl alcohol monomers. Figure 1 discloses a schematic picture of lignin.

In the present application the term “lignin derivative” means molecules or polymers derived from lignin.

In the present application the term “carrier liquid” means an inert hydrocarbonliquid suitable for a hydrotreater or a catalytic cracker (cat cracker) a liquid andmay be selected from fatty acids or mixture of fatty acids, esterified fatty acids,triglyceride, rosin acid, crude oil, mineral oil, tall oil, creosote oil, tar oil, bunker fuel and hydrocarbon oils or mixtures thereof. ln the present invention the “term ““oil” rneans a. nonpolai" chtfnﬁical silbstaiice that is a. vistttïtis liquití at ambifmt teinpeafattlre and. is 'bothl hydrophobic and lipoplïilic. 6 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 solvent orcarrier liquid. The present invention presents a composition and a method ofpreparing said composition Where the composition comprises lignin, Where thecomposition is in liquid phase and may be processed in a refinery such as an oilrefinery. The present invention makes it easier or even facilitates production of fuel from lignin through conventional oil refinery processes.

Lignin In order to obtain lignin biomass may be treated in any suitable Way knoWn to aperson skilled in the art. The biomass may be treated With pulping processes ororganosolv processes for example. Biomass includes, but is not limited to Wood,fruits, vegetables, processing Waste, chaff, grain, grasses, corn, corn husks, Weeds,aquatic plants, hay, paper, paper products, recycled paper, shell, broWn coal, algae,straW, bark or nut shells, lignocellulosic material, lignin and any cellulosecontaining biological material or material of biological origin. In one embodimentthe 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-leaftree. 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 Kappanumber estimates the amount of chemicals required during bleaching of vaofgai. 1311113in order to obtain a pulp With a given degree of Whiteness. Since the amount ofBleach needed is related to the lignin content of the pulp, the Kappa number can beused to monitor the effectiveness of the lignin-extraction phase of the 'jouígaing process. It is approximately proportional to the residual lignin content of the pulp.

Kßc*l 7 K: Kappa number; c: constant = 6.57 (dependent on process and mfc-odﬁ 1: lignincontent in percent. The Kappa number is determined by ISO 302:2004. The kappanumber may be 20 or higher, or 40 or higher, or 60 or higher. In one embodimentthe kappa number is 10-100.

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 invention may comprise black or red liquor, or lignin obtained from black or red liquor.

The alkali aqueous lignin solution may be membrane f1ltrated prior todepolymerization. The membrane filtration may be performed using one or moremembranes with different cut offs. Depending on the cut off of the membrane the permeate or the retentate is collected and depolymerized.

The alkali aqueous lignin solution may be solution obtained from a pulp mill forexample black or red liquor. Black liquor comprises four main groups of organicsubstances, around 30-45 weight% ligneous material, 25-35 weight% saccharineacids, about 10 weight% formic and acetic acid, 3-5 weight% extractives, about 1weight% methanol, and many inorganic elements and sulphur. The exactcomposition of the liquor varies and depends on the cooking conditions in theproduction process and the feedstock. Red liquor comprises the ions from thesulfite process (calcium, sodium, magnesium or ammonium), sulfonated lignin, hemicellulose and low molecular resins.

Lignin derivative The lignin derivative according to the present invention is a depolymerized ligninhaving a molecular weight (MW) of 250-650g/ mol. In one embodiment the molecularweight is 270g/mol or higher, or 300g/mol or higher, or 330g/mol or higher, or360g/mol or higher, or 600g/mol or less, or 550g/mol or less, or 500g/mol or less,or 480g/mol or less, or 450g/mol or less, or 400g/mol or less. The polydispersity is preferably lower than 5, preferably lower than 3, even more preferably lower than 2.

Molecular weight in the present application is determined using GPC (Gel Permeation Chromatography) operated at 20°C and at ﬂow rate of 1 ml/ min using 8 THF as solvent. Polystyrene Standard RedayCal Set M(p) 250-70000 (16 standards)(Sigma product no: 76552). The columns are Styragel THF (pre-column), StyragelHR 3 THF (7.8x3OO mm), Styragel HR 1 THF (7.8x3OO mm), Styragel HR 0.5 THF(7.8x3OO mm) all from Waters.

The lignin derivative according to the present invention has a low oxygen contentsuch as 10% or less, or 9% or less, or 8% or less, or 7% or less, or 6% or less, or 5%or less. The lignin derivative may have the following element content: carbon 70-90%, such as 75-85%, or 80-83%, hydrogen 5-12%, such as 6-9%, nitrogen O-O.5%such as O.1-O.2%, oxygen 3-10% such as 4-8% or 5-7%, sulfur O-1% such as 0.4-O.8%. Since metal residues from the cooking chemicals are not wanted in therefinery process the metal content should be as low as possible. The ligninderivative according to the present invention may have a calcium content of O-70ppm such as 40ppm or less for example 10-30ppm, iron O-50ppm such as30ppm or less for example 10-20ppm, potassium O-50ppm such as 30ppm or lessfor example 10-20ppm, magnesium O-300ppm such as 200ppm or less for example50-150ppm, sodium O-600ppm such as 500ppm or less for example 100-400ppmor 200-300ppm. The ICP analysis (elemental analysis) is done by extraction usingethyl acetate and wherein the ethyl acetate is removed by evaporation leaving driedlignin derivative. An advantage of the present invention is that the lignin in thecomposition does not have to be hydrotreated during the depolymerization step or in an additional step in order to become soluble in a carrier liquid.Solvent According to the present invention the composition comprises a solvent for examplea carrier liquid or an organic solvent or a mixture of a carrier liquid and an organicsolvent. The carrier liquid may be an oil may be any suitable oil for example ahydrocarbon oil, crude oil, bunker oil, mineral oil, tall oil, creosote oil, tar oil, fattyacid or esterified fatty acid. In one embodiment the carrier liquid is a fatty acid or amixture of fatty acids. The fatty acid may be a tall oil fatty acid (TOFA) or ref1ned ordistilled TOFA. In another embodiment the carrier liquid is esterified fatty acidssuch as FAME (fatty acid methyl ester) or triglyceride. In one embodiment thecarrier liquid is a crude oil. In one embodiment the carrier liquid is bunker fuel orbunker 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 9 and a mineral oil, hydrocarbon oil, bunker fuels or crude oil. In anotherembodiment the carrier liquid is a miXture of a hydrocarbon oil or a mineral oil anda fatty acid. In one embodiment the carrier liquid is creosote oil or tar oil. Since thecomposition may be used for preparing fuels the carrier liquid does not have to bean already hydrotreated or cracked liquid such as diesel, instead the carrier liquidshould be a liquid that may be hydrotreated or cracked in a refinery process inorder to form fuel. By using a non-hydrotreated or non-cracked carrier liquidconventional refinery processes may be used and carrier liquids that any Way Would be refined can be used.

The carrier liquid should preteralëljy' be suitable for a hydrotreater or a catalyticcracker (cat cracker), preferably a liquid suitable for both hydrotreater and catalyticcracker. Hydrotreating and catalytic cracking are common steps in the oil ref1neryprocess Where the sulfur, oxygen and nitrogen contents of the oil is reduced andWhere high-boiling, high molecular Weight hydrocarbons are converted into gasoline, diesel and gases.

'Fhff esteifified fatty acid inay be any -sztiitable fatty' acid tfsttfriﬁsfd xtfith any suitablegroup. The fatty acid used in the present invention (as fatty acid or as esterifiedfatty acid) may be a CS or longer fatty acid, or a C14 or longer fatty acid. 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 50Wt%. In one embodiment the carrier liquid is a tall oil or crude tall oil (CTO). Whenthe carrier liquid is a miXture of an oil (hydrocarbon oil, mineral oil, crude oil orbunker fuel) and a fatty acid or esterified fatty acid the ratio in said miXture may bein the range 1-99 Wt% fatty acid (or esterified fatty acid) and 1-99 Wt% of the oil, forexample 20-40 Wt% fatty acid (or esterified fatty acid) and 60-80 Wt% of the oil(hydrocarbon oil, mineral oil, crude oil or bunker fuel). In one embodiment thecarrier liquid comprises 1-15 Wt% esterified fatty acid, such as 2-10 Wt% or 3-6Wt%.

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 likevvise e.g. light cycle oil(LCO), Full Range Straight Run Middle Distillates, Hydrotreated, Middle Distillate,Light Catalytic Cracked Distillate, distillates Najahtha íull--retrige straight-attan, hydroclesißifiirized fiiil-range, solvent-cleﬁwfaxed strziíght-rzinge, straight-rim micE-:ilesiilienjfiated, Plaplitiïa cleiy--treatecl 1ï1l1--range stiraiglrit ruri, clistillates fiill--range arm,disïïillaies iriyrirrpiireaiiecïi iïllí-rarige, stra.ighi-r'i.i1:i. light, cíístillëfies heavy' stifaigliii-riiri,disïíillaies (oi1 saruïi), siïraigli“r_-rii.ri rriifídíe-ruri, Naphïiliëi (siiaie oi1), 1^i§fdrocrarrkeai,fiill-reirige siraiglfit run (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, 101316-57-8,1013 16-539, 9 1722-55-13, 91995--58-6, 63527--21-9, 128683--26--1, 9 199151-4643,öêšf-'ä-íiä--ÛST-ifš, 6$9l5--96--ëš, 1286813--27-2, lššäﬂi-Síš--lêš--â-F). In one embodiment the hydrocarbon oil is a gas oil such as light gas oil (LGO).

Bunker fuel or bunker crude are fuel mainly used for ships, usually very largeships. The bunker fuel may be divided into groups depending on if the fuel is adistillate or a residual or a mixture of both and the chain length. For example No. 1fuel oil is a distillate With a chain length of 9-16, No. 2 fuel oil (also known asBunker A) is a distillate with a chain length of 10-20, No. 4 and No. 5 fuel oil (alsoknown as Bunker B) is a distillate and a residual oil respectively With a chain lengthof 12-70 and No. 6 fuel oil (also known as Bunker C) is a residual (heavy fuel oil)with a chain length of 20-70. No. 5 and 6 are also known as heavy fuel oil (HFO) orfurnace fuel oil (FFO). In one embodiment the bunker fuel is a Bunker B. In anotherembodiment the bunker fuel is a HFO or Bunker C. By adding lignin derivative to the bunker fuel the fuel becomes more environmentally friendly.

The corripcvsitiiëri niay* coirrlrßirise 10-99 'iveiglitïß of carrier liquid of the total *vif-eigiit of”the coniposititin, such as 20 weightïß or iriore, or 40 iveigívrifšê or inore., or 60yifeightO/ši or more, or 80 vifeightfëê or more, or 99 mfeíglitíﬂê or less, or 85 iveightïí» orless, or 65 yveightW-i or less. In one embodinient the anioiirit of carrier liquid is 60- 90 'vifeightWfi such as 65-85 iafeiglitfrfä.

The solvent may also be an organic solvent or a mixture of organic solvents. In oneembodiment the solvent is a mixture of an organic solvent and a carrier liquid. Theorganic 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-C10esters. A non-limiting list of 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 11 glycol, 1,4-dioxane and tetrahydrofuran, methylated tetrahydrofuran, mesityl oxide,furfural, isophorone. Preferred C2-C1O esters are organic esters, aromatic or non-aromatic esters, examples of esters are benzyl benzoate, various acetates such asmethyl acetate, ethyl acetate, cyclopentyl methyl ether and butyl acetate, variouslactates such as ethyl lactates. Solvents that are similar to or may be converted intofuel or petrol are interesting When the composition is to be used for fuelpreparation. Such solvents could be ketones or aldehydes. In one embodiment thesolvent is a C2-C15 ketone such as a C4-C12 ketone or a C6-C8 ketone. In oneembodiment the solvent is a Cl-C10 aldehyde such as a C4-C9 aldehyde or C6-C8aldehyde. In one embodiment the solvent is a mixture of a C2-C15 ketone and a C1-C1O aldehyde. In one embodiment the solvent is mesityl oxide. In one embodimentthe solvent is acetone. In one embodiment the solvent is acetophenone. In oneembodiment the solvent is pentanone. In one embodiment the solvent is ethylisopropyl ketone. In one embodiment the solvent is isophorone. In one embodimentthe organic solvent is an aromatic aldehyde or a mixture containing an aromaticaldehyde for example furfural. In one embodiment the solvent comprises furfural orfurfuryl alcohol. In one embodiment the solvent is benzaldehyde. In oneembodiment the solvent is ethyl acetate. In one embodiment the solvent is a Cl-C10alcohol. In one embodiment the solvent is ethanol. In one embodiment the solvent ismethanol. In one embodiment the solvent is isopropanol. In one embodiment thesolvent is solketal. In one embodiment the solvent is a C2-C1O ester. In oneembodiment the solvent is tetrahydrofuran or methylated tetrahydrofuran. In one embodiment the solvent is 1,4-dioxane.

In one embodiment the solvent comprises a combination of Cl-C10 alcohols, C2-C1O ethers and C2-C1O esters. In one embodiment the solvent comprises two C1-C1O alcohols for example ethanol and glycerol, and in another embodiment thesolvent comprises propanol and glycerol. In one embodiment the solvent comprisespolyethylene glycol and a Cl-C10 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.

In one embodiment the solvent is a mixture of a C2-C15 ketone such as a C4-C12 ketone or a C6-C8 ketone or a Cl-C10 aldehyde such as a C4-C9 aldehyde or C6- 12 C8 aldehyde and a carrier liquid. In one embodiment the solvent is a miXture of a Cl-C10 alcohol such as a C3-C8 alcohol and a carrier liquid.

In one embodiment the amount of added organic solvent in the composition is 1-99weight% of the total weight of the composition. In one embodiment the amount ofsolvent is 1-60 weight%, or 5-50 weight%, or 10-30 weight%. In one embodimentthe amount of organic solvent is 70 weight% or less, or 40 weight% or less, or 20weight% or less, or 10 weight% or less, or 5 weight% or less, or 2 weight% or less,or 1 weight% or less of the total Weight of the composition. In one embodiment thecomposition comprises 0.1-1wt% of ethanol, for example 0.2 to 0.5wt%. In oneembodiment the composition is essentially free from any added organic solvents.Organic solvents and water may have a negative effect when the composition istreated in a refinery for example it may harm the catalysts or the products may beoxidated and therefore the concentration of organic solvent or water should in some applications be kept as low as possible.

Preparation of the composition The present inventors found that by depolymerizing the lignin to small polymeric oroligomeric fractions the solubility of the lignin increased drastically in more non- polar solvents and even in lipophilic solvents such as oils.

The composition according to the present invention may be prepared by firstpreparing the lignin derivative followed by miXing said modified lignin with thesolvent. The lignin derivative may be isolated from the depolymerization reactionmiXture or the lignin derivative may be left in the reaction miXture when mixed withthe carrier liquid. The depolymerization of the lignin may also be performed in thepresence of the carrier liquid. The miXing can be done by stirring or shaking or inany other suitable way and the slurry is then heated. Any catalyst and any other unwanted components may be removed afterwards using any suitable technique.

The depolymerization of the lignin is preferably a thermal depolymerization processwhere temperature and pressure facilitates the depolymerization of the lignin. Noadded catalyst, such as transition metal catalysts, is necessary. Without beingbound be theory but the cooking chemicals, the salts or the base, present in theblack or red liquor, are believed to be important. Studies performed by the present inventors have shown no or very low depolymerization when the thermal treatment 13 is performed in pure water. The depolymerization may be performed at 270°C orhigher, or 300°C or higher, or 310°C or higher, or 320°C or higher, or 330°C orhigher, or 340°C or higher, or 350°C or higher, but preferably not higher than500°C, or 450°C or lower, or 420°C or lower, or 400°C or lower, or 370°C or lower,or 360°C or lower. The thermal treatment time depends on the volume of the liquor to be treated.

The pressure in the sealed container may be 5bar or higher, or lObar or higher, or20bar or higher, or 30bar or higher, or 40bar or higher, or 50bar or higher, or60bar or higher, but preferably not more than 200bar, or 180bar or lower, or150bar or lower, or 120bar or lower, or lOObar or lower, or 80 bar or lower, or 65 bar or lower.

Before the thermal depolymerization process the alkali aqueous lignin solution (forexample black liquor) may be diluted in order to decrease the concentration. Adecrease in concentration results in less char formation. A preferred concentrationof solid content in the aqueous lignin composition may be 15 weight% or less, suchas 10 weight% or less. The present inventors found that by using weak liquor orthin liquor the char formation was reduced in comparison when using concentratedblack liquor or thick black liquor. Weak or thin liquor is black liquor obtained fromthe digester prior to any evaporation (concentration around 15-20 weight%) whileconcentrated or thick black liquor is liquor obtained after evaporation (concentration around 55-80 weight%).

After the thermal treatment an organic phase and an aqueous phase are formed aswell as solid residues. The organic phase comprises the lignin derivative and thelignin derivative may be isolated using any suitable technique such as liquid / liquideXtraction, decantation evaporation or centrifugation. The obtained lignin derivativeis also deoxygenated. Liquid / liquid extraction may be performed using for exampleethyl acetate, dichloromethane or toluene as extracting solvent. The aqueous phasemay comprise lignin or lignin derivatives not soluble in carrier liquids. When theorganic phase has been removed the aqueous phase may be thermally treated againusing the same conditions or different conditions as in the first thermal treatmentstep. In another embodiment the aqueous phase may be hydrotreated using ahydrogen donor such as hydrogen gas or formic acid in order to make the lignin or lignin derivatives more soluble in carrier liquids. The obtained hydrotreated lignin 14 or lignin derivatives may be mixed with a carrier liquid and/ or combined with theorganic phase of the first thermal treatment or the isolated lignin derivative of thefirst thermal treatment. The hydrotreatment step may be conducted as explained below.

The present inventors surprisingly found that by adding small amounts of ethanolto the black or red liquor prior to depolymerization step the amount of char formed was significantly reduced.

The yield of lignin derivative after the thermal depolymerization may be 30-70%, or40-60%. Since the amount of lignin in black liquor is hard to determine the amount of lignin obtained by acid precipitation is considered 100% yield.

One advantage of the present invention is that a high amount of lignin may bedissolved in a carrier liquid without any use of organic solvents or modif1cations ofthe lignin. The amount of lignin derivative in the composition according to thepresent invention may be 1 weight% or more, or 2 weight% or more, or 4 weight% ormore, or 5 weight% or more, or 7 weight% or more, or 10 weight% or more, or 12weight% or more, or 15 weight% or more, or 20 weight% or more, or 25 weight% ormore, or 30 weight% or more, or 40 weight% or more, or 50 weight% or more, or 60weight% or more, or 70 weight% or more, or 80 weight% or more, or 90 weight% ormore. In one embodiment the lignin content is 20-60 weight% such as 30-50weight% or 35-45 weight%. High amounts of lignin in the composition increases theviscosity of the composition making it hard to pump and treat. The lignin in thecomposition is non-hydrotreated and still shows high solubility in carrier liquids this is believed to be a result of low oxygen content and the molecular weight.

Any cooking chemicals separated from the lignin derivative composition may bereturned to the recovery boiler of the pulp mill. The present method may be integrated into a pulp mill process or into a fuel refinery process.

The composition according to the present invention may be a one phase system. Bykeeping the composition in motion continuously or regularly the composition maystay in one phase for a prolonged time. Since the composition is meant to be usedfor example in a refinery the composition will be in motion and thereby it will be a one phase system. In one embodiment the composition is a one phase system at 70°C, preferably also at 25°C, When left for 10 minutes, preferably 30 minutes,preferably 1 hour, preferably When left for 24 hours.

Applications The present invention may be used for preparing fuel or fuel additive. Thecomposition according to the present invention may itself be used as a fuel additive.It is believed that the lignin derivative in the composition according to the presentinvention requires less hydrogen than if lignin Would be hydrotreated for example ina slurry cracker or hydrotreatment of functionalized lignin (alkylated lignin via esterif1cation for example) dissolved in a carrier liquid.

The composition according to the present invention may be used in a refineryprocess or in a pre-step to a refinery process for preparing fuel such as diesel andpetrol, or diesel and petrol analogues; or biogasoline or biodiesel; or fuel additives.The composition may be treated in a hydrotreater or in a catalytic cracker such asan FCC. The composition may further be used to prepare lubricants or oils. For example synthetic oils With boiling point of at least 359°C.

One method of preparing fuel from lignin or lignin derivative that is not soluble in acarrier liquid may comprise dissolving lignin or lignin derivative in an organicsolvent and then hydrotreat the obtained solution, fully or partially. Any suitablesolvent as described above may be used. Hydrotreated lignin soluble in a carrierliquid is then transferred or added to a carrier liquid before treated in a catalytic cracker for example.

During hydrotreating the feed may be exposed to hydrogen gas (for example 20-200bar) and a hydrotreating catalyst (NiMo (Nickel Molybdenum), CoMo (CobaltMolybdenum) or other HDS, HDN, HDO catalyst) at elevated temperatures (200-500°C). The hydrotreatment process results in hydrodesulfurization (HDS),hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) Where the sulphurs,nitrogens and oxygens primarily are removed as hydrogensulfide, ammonia, and Water. Hydrotreatment also results in the saturation of olefins.

Catalytic cracking is a category of the broader refinery process of cracking. Duringcracking, large molecules are split into smaller molecules under the influence of heat, catalyst, and/ or solvent. There are several sub-categories of cracking Which 16 includes thermal cracking, steam cracking, ﬂuid catalyst cracking andhydrocracking. During thermal cracking the feed is exposed to high temperaturesand mainly results in homolytic bond cleavage to produce smaller unsaturatedmolecules. Steam cracking is a version of thermal cracking where the feed is dilutedwith steam before being exposed to the high temperature at which cracking occurs.In a ﬂuidized catalytic cracker (FCC) or “cat cracker” the preheated feed is mixedwith a hot catalyst and is allowed to react at elevated temperature. The mainpurpose of the FCC unit is to produce gasoline range hydrocarbons from differenttypes of heavy feeds. During hydrocracking the hydrocarbons are cracked in thepresence of hydrogen. Hydrocracking also facilitates the saturation of aromatics and olefins.

The hydrotreatment may involve treating the lignin with hydrogen gas or ahydrogen donor in order to obtain a fully or partially hydrogenated product. Thehydrogen donor may for example be formic acid or an alcohol or a combinationthereof. Suitable alcohols are methanol (MeOH), ethanol (EtOH), propanol, iso-propanol (i-PrOH), glycerol, glycol, butanol, t-butanol (i-BuOH) or combinationsthereof. The pressure during the hydrotreatment may be 5 to 400 bar such as 50bar or higher, or 100 bar or higher, or 300 bar or lower, or 200 bar or lower. Thehydrotreatment may be mild due to the lower oxygen content and therefore thehydrogen pressure may be 30-70 bar such as 40-60bar. Since water is generatedduring the hydrogenation a large amount of energy is released. By using a lowhydrogen gas pressure this issue may be handled. The hydrotreatment may beperformed at a temperature of not more than 400°C, preferably not more than300°C, or not more than 200°C. If the lignin is depolymerized a mildhydrotreatment may be sufficient to increase the solubility in carrier liquids inother words treating the lignin derivative at a temperature under 400°C, or under 300°C, and at a pressure less than 50 bar.

The hydrotreatment may be performed in the presence of a catalyst for example atransition metal catalyst such as an Al, W, Ir, Re, Ni, Mo, Zr, Co, Ru, Rh, Pt or Pdbased catalyst. For example Raney nickel, nickel on carbon, Ni/ Si, Ni / Fe, Nickelnanopowder, zeolite, amorphous silica-alumina, Pd/ C, NiMo or CoMo or acombination thereof. The most common catalysts are a NiMo or a CoMo catalyst or a combination thereof. 17 The hydrotreatment may be repeated or a new hydrotreatment step may beperformed at other conditions. For example in a first hydrotreatment step the ligninor lignin derivative may be hydrotreated at a temperature of not more than 200°Cand at a pressure of less than 40 bar. Then, any hydrotreated lignin or ligninderivative that has become soluble in a carrier liquid may be separated out and theremaining lignin or lignin derivative may then be hydrotreated in a second step, forexample at a temperature of not more than 300°C and at a pressure of less than 80bar. This procedure may be repeated using the same conditions or the temperatureand/ or pressure may be increased for each additional step. After eachhydrotreatment step hydrotreated products may be extracted using liquid-liquidextraction using any suitable solvent such as ethyl acetate, phenol, toluene or acarrier liquid such as fatty acids or oils, or the hydrotreated products may beseparated using filtration or membrane filtration or acid induced precipitation orcombination thereof. The hydrotreated products may also be isolated or separatedby distillation. During the hydrotreatment hydrogen gas is preferably used but formic acid may also be used.

The hydrotreated product may be further treated in a catalytic cracker or used asfuel or a fuel additive. Any cooking chemicals isolated from the process may be returned to the recovery boiler of the pulp mill plant.

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 inasphalt, emulsifying agent, fiber strengthening additive, cross-linking agent, boardbinder, anti-corrosion additive, Wear resistant additive, antifriction additive, binder, emulsif1er or dispersing agent or for preparing tyres.

The composition may further be used to prepare foams, plastics, rubbers or paint.The esterif1ed 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 beenhanced by the use of the composition. The composition may further be used as araw material for preparing fine chemicals such as aromatic compounds using conventional techniques.

The composition may be added to surfaces to obtain dust control, or the composition may be used to prepare batteries. 18 EXAMPLESExample 1General procedure of hydrothermal treating: A 10 ml Stainless steel (316) reactor Was charged With black liquor (5-6 g) and insome cases With an additive. The reactor Was sealed and heated in a pipe oven for 1hour at 300, 320 or 340 °C. After cooling in a stream of air the reactor Was opened and the contents Were treated according to the Work up procedures below.The products Were analyzed With GPC, NMR, MALDI-TOF and GC-MS.Work up procedure A: The reaction miXture Was extracted 3 times With ethyl acetate. A layer separationWas achieved in a centrifuge and the organic phase Was removed and combined.The combined organic phases Were dried over Na2SO4 and evaporated to give an oil.The aqueous solution Was filtered and the retentate Was Washed With Water and dried. The aqueous phase Was evaporated and dried at 60 °C.Work up procedure B: As in the Work up procedure A, but instead of f1ltering the aqueous phase it Wasfirst acidified With conc. HCl to pH 2 and extracted 2 times With ethyl acetate. Theethyl acetate extracts Were dried over Na2SO4 and evaporated. The aqueous solution Was filtered and the retantate Was Washed With Water and dried.Work up procedure C: The reaction miXture Was transferred With ethyl acetate and Water to a 50 ml testtube and acidified With HCl to a pH of 2. After repeated extraction (3 times in total)the combined organic extracts Were dried over Na2SO4 and evaporated. The aqueous phase Was filtered, the insolubles Were Washed With Water and dried.Work up procedure D:The reaction miXture Was filtered and the solid material Was Washed With Water.

Distillation of the hydrothermal product: 19 The hydrothermal oil from the Work up procedure A (639 mg) Was distilled With aKugelrohr apparatus to give 348 mg dark yellow oil and 183 mg residue.

Solubility determination: A carefully Weighted sample of the substrate (100 mg) Was measured in an HPLC-vial. A carefully Weighted amount of solvent (100 mg) Was added, the vial Wascapped and shaken for 30 minutes at 70 °C. After cooling to room temperature thePTFE-cap Was changed to a cap With a paper filter and the vial Was placed upsidedown into a conical 15 ml polypropylene plastic tube. The assembly Was centrifugedfor 5 minutes to filter off the solution. The approximate value of solubility could becalculated from the amount of the obtained solution, Table 1.

Table 1. Solubility results of organic phase in different solvents (carrier liquids).

Solvent VïSCOSílïY (CSÛ Solubles (Wt%) Conc. of LD (Wt%)LGO 72.3 42.1LGO 68.2 39.7LGO 74.3 42.7 FAME 94.0 48.5LCO 90.0 46.2VGO 43.8 29.9VGO, 10 79.4 44.3LGO, 75.3 42.9LGO” 75.0 42.9 TriglycerideTOFA 92.5 47.9327 TOFAíLGO 83.7 44.1 LD=lignin derivative, LGO=Light Gas Oil, VGO=Vacuum Gas Oil, FAME =Fatty AcidMethyl Ester, LCO = Light Cycle Oil, TOFA=Ta1l oil fatty acid LGO and LGO' as Well as VGO, VGO' and VGO” refers to different brands or types of the same class of oil.

Example 2 Different black liquors Were tested using the method according to the presentinvention - Weak (f1r), concentrated (broadleaf) and a miXture of weak andconcentrated (fir/broadleaf). The effect of an added alcohol (ethanol or methanol) Was also studied. 3-5g of black liquor With or Without alcohol Was heated in a 10 ml reactor placed ina tube oven at 340°C for one hour. The product Was extracted using ethyl acetate(lst extraction). The remaining aqueous solution Was acidified and extracted Withethyl acetate again (Qnd extraction). The remaining aqueous solution Was filteredand the obtained solid material (char) Was dried. The presented results are in percent of lignin mass in the black liquor, Figure 3 and 4.

Addition of an alcohol, especially ethanol, resulted in a significant decrease in char formation.Example 3Substance: Sample 1 organic phase -EtOAc extracted and dried Elementary analysis: Carbon 82.03%Hydrogen 7.98%Nitrogen 0.12%Oxygen 653%Sulfur 0.68% Table 2. ICP results.Ca 396.847 Fe 259.941 K 766.491 Mg 279.553 Na 589.592 S 180.731 199m ppm ppm ppm ppm 533mRFAPZe 163t3 org 24.6 15 17 114 346 6753RFAPEQ 163t3 resid ue 756 4118 589 1148 9590 9087RFA P26: 163123 aq 90.8 27 17664 43 416171 8766 RFAP1e163t3 org = product from first extraction With ethyl acetateRFAP2e163t3 residue =coke RFAP2e163t3 aq = evaporated aqueous phase Conclusion: Most of the sodium is in the aqueous phase together With the cokes. The oxygen content is only 6% in comparison With in black liquor Where it is 30%. 21 70-80% of the organic phase is soluble in light gas oil (LGO) as seen in the table belowExample 4 A 10 ml stainless steel (316) reactor Was charged With black liquor. The reactor Wassealed and heated in a pipe oven for 1 hour at 270°C. After cooling in a stream ofair the reactor Was opened and the contents Were treated according to the Work up procedures below.

The products Were analyzed With GPC, MALDI-TOF and GC-MS.

BL source Arnount Lignin conc. 1st extr 2nd extr Char 1st extr 2nd extr Char(g) (°/°) (mg) (mg) (mg) (°/°) (°/°) (°/°) ﬁr 6 6.76 139 91 65.8 34.3 22.4 16.2 ﬁr 6 6.76 142 80 74.9 35.0 19.7 18.5

Claims

1. A composition comprising lignin derivative and a solvent; Wherein the lignin derivative has a Weight average molecular Weight (MW) of 250g/mol to 650g/mol.

2. The composition according to claim 1 Wherein the solvent is a carrier liquid.

3. The composition according to claim 1 or 2 Wherein content of lignin derivative is1 Weight% or more, or 2 Weight% or more, or 4 Weight% or more, or 5 Weight% ormore, or 7 Weight% or more, or 10 Weight% or more, or 12 Weight% or more, or 15Weight% or more, or 20 Weight% or more, or 25 Weight% or more, or 30 Weight% ormore, or 40 Weight% or more, or 50 Weight% or more, or 60 Weight% or more, or 70 Weight% or more, or 75 Weight% or more.

4. The composition according to any one of claims 1-3 Wherein the content ofsolvent is at least 20 Weight%, or at least 30 Weight%, or at least 40 Weight%, or atleast 50 Weight%, or at least 60 Weight%, or at least 70 Weight%, or at least 80Weight%, or at least 90 Weight% of the total composition.

5. The composition according to any one of claims 1-4 Wherein the content of lignin derivative is 20 Weight% or more and Wherein the solvent is a carrier liquid.

6. The composition according to any one of claims 1-5 Wherein the Weight average molecular Weight (MW) is 300g/mol to 500g/ mol.

7. The composition according claim 2 Wherein the carrier liquid is a hydrocarbon oil, crude oil, bunker oil or mineral oil.

8. The composition according to claim 1 Wherein the solvent is selected from 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.

9. The composition according to claim 1 Wherein the composition further comprises 0.1 to 1Wt% of added ethanol. 23

10. The composition according to claim 2 Wherein the carrier liquid is tall oil, creosote oil, tar oil, fatty acid or esterified fatty acid.

11. The composition according to claim 2 Wherein the carrier liquid is a miXture of a hydrocarbon oil and a fatty acid or an esterified fatty acid.

12. The composition according to claim 2 Wherein the solvent is a carrier liquid andthe lignin derivative has a content of carbon of 70-90%, such as 75-85%, or 80-83%, hydrogen 5-12%, such as 6-9%, nitrogen O-O.5% such as 0.1-O.2%, oxygen 3-10% such as 4-8% or 5-7%, sulfur O-1% such as O.4-O.8%.

13. The composition according to claim 1 Wherein the solvent is an organic solventand the lignin derivative has a content of carbon of 70-90%, such as 75-85%, or 80-83%, hydrogen 5-12%, such as 6-9%, nitrogen O-O.5% such as 0.1-O.2%, oxygen 3-10% such as 4-8% or 5-7%, sulfur O-1% such as O.4-O.8%.

14. A method of producing the composition according to any one of claims 1 to 13 comprising: -adding an alkali aqueous lignin solution to a container; -sealing the container; -heating the black or red liquor to at least 270°C to depolymerize the lignin to amolecular Weight of 250-650g/ mol; and -miXing the depolymerized lignin With a solvent.

15. Use of the composition according to any one of claims 1 to 13 for preparing fuelsuch as petrol and diesel, or diesel and petrol analogues, or biogasoline or biodiesel; or fuel additives. 24

16. A method of preparing fuel comprising treating the composition according to any one of claims 1 to 13 in a hydrotreater or a catalytic cracker.

17. A fuel obtained by hydrolytical cracking or hydrotreatment of the composition according to any one of claims 1 to 13.

18. A fuel additive comprising the composition according to any one of claims 1 to 13.

19. A fuel comprising the composition according to any one of claims 1 to 13.

20. Use of the composition according to any one of claims 1 to 13 for producing chemicals or paint or tyres.

21. Use of the composition according to any one of claims 1 to 13 as concretedgrinding aid, set retarder for cement, strengthener of cement, antioxidant, enhancerof thermal protection, stabilizer in asphalt, emulsifying agent, f1ber strengtheningadditive, cross-linking agent, board binder, anti-corrosion additive, Wear resistantadditive, antifriction additive, binder, emulsifier or dispersing agent, cross-linkingor curing agent, or as a Water absorption inhibitor or as a ﬂuidization agent, as ananti-bacterial or anti-fungal surface or as a barrier, to impregnate Wood or as an anti-corrosion agent.