SE1551502A1 - Process for making lignin composition - Google Patents

Abstract

17 AB STRACT The invention relates to a process for making a purified lignin CompositionComprising a Carrier liquid suitable for processing in a refinery. It Comprisesproviding an aqueous lignin Composition Comprising lignin, Cooking ChemiCals andWater and adding a Carrier liquid to the aqueous lignin to provide an organiCphase. Then all or substantially all the Water is removed from the Composition. Thelignin Composition is proCessed to make the lignin more soluble in the Carrier liquidin order to transfer more of the lignin to the organiC phase. Cooking ChemiCals areremoved, suitably by of Washing by liquid / liquid eXtraCtion using a Washing liquid. Finally Washing liquid is removed. (Fig. 1)

Description

PROCESS FOR MAKING LIGNIN COMPOSITION The present invention relates to processes for providing lignin based feedstock forref1neries, and in particular to a composition suitable for direct inclusion in a ref1nery process.

Background of the Invention 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 ofthe biomass. Lignin comprises chains of aromatic and oxygenate constituentsforming larger molecules that are not easily treated. A major reason for difficulty intreating the lignin is the inability to disperse the lignin for contact with catalysts that can break the lignin down.

Lignin is one of the most abundant natural polymers on earth. One common way ofobtaining 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 methoxygroups and the phenolic and aliphatic hydroXyl groups provide sites for e.g. furtherfunctionalization. Lignin is known to have a low ability to adsorb 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. Lignin hashigher energy content than cellulose or hemicelluloses and one gram of lignin hason average 2.27 kJ, which is 30% more than the energy content of cellulosiccarbohydrate. The energy content of lignin is similar to that of coal. Today, due toits fuel value lignin that has been removed using the Kraft process, sulphateprocess, in a pulp or paper mill, is usually burned in order to provide energy to run the production process and to recover the chemicals from the cooking liquor.

There are several ways of separating lignin from black or red liquor obtained afterseparating the cellulose fibres in the Kraft or sulphite process respectively, duringthe production processes. One of the most common strategies is membranefiltration. LignoBoost® is a separation process developed by Innventia AB and theprocess 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 (CO2), and the lignin is then filtered off. The lignin filter cake isthen re-dispersed and acidified, usually using sulphuric acid, and the obtainedslurry is then filtered and washed using displacement washing. The lignin isusually then dried and pulverized in order to make it suitable for lime kiln burners or before pelletizing it into pellet fuel.

Biofuel, such as biogasoline and biodiesel, is a fuel in which the energy 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 low solubility of lignin in organic solvents. One drawback of using lignin as a source for fuel production is the issue of providing lignin or lignin derivatives in a formsuitable for hydrotreaters or crackers. The problem is that lignin is not soluble inoils 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. A11 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.

Applicants own WO 2015/ 094099 relates to a composition comprising a highcontent of lignin or lignin derivatives in a fatty acid, esterified fatty acid or oil andoptionally an organic solvent as well. In order to obtain a high content of lignin ithas to be functionalized or modified by e.g. esterification of the hydroxyl groups.One application for the composition may be as a raw material for fuel production or for the preparation of lubricating oils.

Summary of the Invention In order to be usable as a feed-stock for refineries a lignin composition must beprovided that is compatible With the process media in the refinery, and this requiresthat it is essentially water-free and essentially free from any residues of cooking chemicals when black liquor is used as raw material.

The object of the present invention is therefore to provide an improved process formaking a lignin composition suitable for processing in a refinery, which meets the above requirements.

This object is met by the process defined in Claim 1.

It Comprises a process for making a purif1ed lignin Composition Comprising a Carrierliquid suitable for processing in a refinery. It Comprises providing an aqueouslignin Composition Comprising lignin, Cooking ChemiCals and Water and adding aCarrier liquid to the aqueous lignin to provide an organiC phase. Then all orsubstantially all the Water is removed from the Composition. The lignin Compositionis proCessed to make the lignin more soluble in the Carrier liquid in order totransfer more of the lignin to the organiC phase. Cooking ChemiCals are removed,suitably by of Washing by liquid / liquid eXtraCtion using a Washing liquid. Finally Washing liquid is removed.

Preferred embodiments are defined in the dependent Claims.

Further sCope of appliCability of the present invention Will beCome apparent from the detailed desCription given hereinafter and the aCCompanying dravvings WhiCh are given by Way of illustration only, and thus not to be Considered limiting on the present invention, and Wherein Fig. 1 is a sChematiC illustration of the new proCess; Fig. 2 is a sChematiC illustration of one embodiment; Fig. 3 is a sChematiC illustration of another embodiment; and Fig. 4 is a sChematiC illustration of embodiments of a final Washing step.

Detailed Description of Preferred Embodiments In the present appliCation the term “lignin” means a polymer Comprising Coumaryl alCohol, Coniferyl alCohol and sinapyl alCohol monomers. Figure 8 disCloses a sChematiC piCture of a part of lignin.

In the present application the term “carrier liquid” means a liquid selected fromfatty acids or mixture of fatty acids, esterified fatty acids, rosin acid, crude oil,mineral oil, bunker fuel and hydrocarbon oils or mixtures thereof. ln the present ínventiflon. the terrn “oiï means a nonpolar trlfiemical Substance that is a víscous liquid at ambient temperature and is “both lïywcírotähaäbic and liggophiliaï.

Fig. 1 is a schematic and generic illustration of the new process.

The schematic illustration is divided in three partitions, A, B and C, wherein Band C represent the claimed generic process. Partition A represents differentkinds of preprocessing 1, 2,....n ofa lignin solution (e.g. black liquor), theresulting product of which will be fed into the novel process. The differentoptions represent different available methods for extracting lignin from thelignin solution (e.g. black liquor, acetosolv, organosolv, red or brown liquor), theresult being an aqueous composition comprising lignin, Cooking Chemicals and water in various Concentrations depending on the method used.

Thus, the first step S1 in the novel process, represented by the arrows LC1,LC2,....LCn, (where LC means “lignin composition) is to supply a suitable reactor vessel RV with a lignin composition with the specified constituents.

In a second step S2 (in partition B) a Carrier liquid (for example an oil or fattyacid) is added to this starting composition to provide an organic phase. A minorfraction of the lignin will dissolve in this organic phase, another fraction mightprecipitate, but the major portion will remain in the aqueous phase. Thus, whatwe have now is a two or three-phase system, i.e. two liquid phases and apossibly solid phase, with lignin and Cooking Chemicals dissolved in an aqueousphase, an organic phase with some lignin dissolved and possibly a ligninchemical precipitate. The precipitated lignin may comprise Cooking Chemicals associated to the precipitated lignin.

In the method according to the present invention a carrier liquid is used, forexample an oil. The carrier liquid may be any suitable oil for example ahydrocarbon oil, crude oil, bunker oil, mineral oil, tall oil, creosote oil, tar oil, fatty acid or esterified fatty acid. In one embodiment the carrier liquid is a fatty acid or a mixture of fatty acids. The fatty acid may be a tall oil fatty acid (TOFA). In anotherembodiment the carrier liquid is esterified fatty acids such as FAME (fatty acidmethyl ester) or triglyceride. In one embodiment the carrier liquid is a crude oil. Inone embodiment the carrier liquid is bunker fuel or bunker crude. In anotherembodiment the carrier liquid is a hydrocarbon oil or a mineral oil. In oneembodiment the carrier liquid is a mixture of esterified fatty acid and a mineral oil,hydrocarbon oil, bunker fuel or crude oil. In another embodiment the carrier liquidis a mixture of a hydrocarbon oil or a mineral oil and a fatty acid. In oneembodiment the carrier liquid is creosote oil or tar oil. Since the composition maybe used for preparing fuels the carrier liquid does not have to be an alreadyhydrotreated or cracked liquid such as diesel, instead the carrier liquid should be aliquid that may be hydrotreated or cracked in a refinery process in order to form afuel. By using a non-hydrotreated or non-cracked carrier liquid conventionalrefinery processes may be used and carrier liquids that any Way Would be refined can be used.

When the carrier liquid is or comprises a hydrocarbon oil the carrier liquid needs tobe in liquid phase below 80 °C and preferably have boiling points of 177-371 °C.These hydrocarbon oils include different types of or gas oils and likewise e.g. lightcycle oil (LCO), Full Range Straight Run Middle Distillates, Hydrotreated, MiddleDistillate, Light Catalytic Cracked Distillate, distillates Flaplïïilïa fïlíl-rz-:uuge stfziíglæt-min, hyfdroclesuífiïrizecl íïlfl-ivaiige, solvent-denvaxe-fi straightfiange, straight-runrrlicíaïilfe sulfenylateaí, Nagahiíhz-:L c:1:-;;y'~1'rea1'e<'í 'íïgzíbrarlge s'ï;raig11t, run, flístíllaftes full-rfinge aim, distillates hydrotreafte-:1 íïlíl-raiïge, straíghïærun light, clistillaftes heavystraíglïtfiïlrï, dísïiíílates (tiil. Samui), st,1:"aigl1ïi-r11r1 rnídfílefiïln, Nagvhtšla. (shale oil),hydrocrzickeci, full-range straight 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, 101318589, 91722-55-3, 91995458-3, 6852742143, 128683-26-1,91.99.5469, 684199543, ñ8915-9ñ-8, 128683-2739, 1.95459-1.9~9). In one embodiment the hydrocarbon oil is a gas oil such as light gas oil (LGO).

Organic solvents that are similar to or may be converted into fuel or petrol maybe added as Well. They are interesting since any residues of the organic solventWill not have any negative effect on the subsequent refinery process. Such solvents could be ketones or aldehydes. In one embodiment the solvent is a C2- C15 ketone such as a C4-C12 ketone or a C6-C8 ketone. In one embodimentthe solvent is a Cl-C10 aldehyde such as a C4-C9 aldehyde or C6-C8 aldehyde.In one embodiment the solvent is a mixture of a C2-C15 ketone and a Cl-C10aldehyde. A non-limiting list of solvents is mesityl oxide, acetone, acetophenone,pentanone, ethyl isopropyl ketone, isophorone, furfural, benzaldehyde or ethyl acetate. These may also be used for washing the organic phase.

Next S3, water is removed, by a suitable method such as heating, evaporation,osmosis, membrane filtration, decanting process, centrifugation or any otherfeasible method. Preferably at least 90%, more preferred more than 95% of thewater, even more preferred more than 99 % of the water is removed. Whenremoving the water by heating or evaporation a substantial portion of the cookingchemicals CC precipitate, schematically shown at the bottom of the reactor vesselRV. Also depending on the method of removing the water, for example heating or evaporation, the lignin dissolved in water will precipitate when water is removed.

It is now desirable to transfer the carrier liquid insoluble lignin, which asmentioned is a major part of the lignin, to the organic phase. This can be done bymodifying the lignin such as by alkylation (e.g. esterification, etherification oramidation), deoxygenation, depolymerization or hydrogenation or protonation of thelignin, schematically indicated With reference S4. Hydrogenation or protonation isperformed preferably using a catalyst, such as transition metal catalysts forexample Pt, Pd, Raney Nickel or Ni on zeolites. Methods usable for this step aredisclosed in applicants own WO 2014/ 039002 A1. The lignin becomes less watersoluble, and instead it will be hydrophobic and therefore it will dissolve in the organic phase.

As described in WO20l5 / 094099 the present inventors found that by esterifyingthe hydroxyl groups of the lignin or lignin derivatives the solubility of the ligninincreased drastically. A lignin composition may be prepared by first preparing theesterified lignin or lignin derivative and then mixing said esterified lignin with acarrier liquid or solvent. A suitable carrier liquid is fatty acid or esterified fattyacid, or a mixture of fatty acid and a hydrocarbon oil. The esterified lignin may beisolated from the esterification reaction mixture or the esterified lignin is left in the reaction mixture when mixed with the carrier liquid or solvent. The esterification of the lignin may also be performed in situ, i.e. in the carrier liquid or solvent. Thenthe lignin, the esterification agent or, the first fatty acid and an esterification agent,and the carrier liquid (or solvent) and optionally a catalyst are mixed to form aslurry or mixture. The slurry or mixture is then preferably heated between 50°Cand 350°C, such as 50°C or higher, or 80°C or higher or 100°C or higher, or 120°Cor higher, or 150°C or higher, but not higher than 350°C, or 250°C or lower, or200°C or lower, or 180°C or lower. The esterification agent may be a carboxylic acidor an anhydride. The esterification agents preferably contain an unsaturated bond.Non-limiting examples of carboxylic acids are fatty acids or C2-C42 carboxylicesters, preferably C4 to C22 such as C18, and non-limiting examples of anhydridesare C4 to C42 anhydrides. The catalyst for the esterification may be a nitrogencontaining aromatic heterocycle such as N-methyl imidazole or pyridine, or the catalyst may be a metal acetylacetonate such as TiO(acac)2 or Fe(acac)3.

When the modification of the lignin is done by etherif1cation the modification agentmay be an epoxide. The epoxide can be an alkyl epoxide for example a C5 or longeralkyl epoxide, or a C12 or longer alkyl epoxide, or C18 or longer alkyl epoxide. Itcould alternatively be a fatty acid epoxide. The etherification may be performed at80°C or higher, or 120°C or higher, or 150°C or higher, or 180°C or higher,preferably at 350°C or lower, or at 250°C or lower, or at200°C or lower .

The precipitated cooking chemicals can now be separated from the organic phasewhich contains the lignin. Such separation can be performed in a number of ways, which will be disclosed in greater detail below.

The separated cooking chemicals are preferably returned (dashed arrow R1) to thepulping process whereby the economy of the over-all process is considerably improved.

The lignin composition now comprising modified lignin dissolved in an organicphase and possibly some residual water and cooking chemicals (CC) is nowpreferably subjected to a further washing step S5 using an aqueous medium,preferably an aqueous acid or a ligand/ chelating solution (e.g. EDTA), in order to remove CC, metal ions and electrostatically bound metal ions from the lignin. The Washing is suitably performed as a liquid/ liquid extraction, e.g. in a scrubber or by mixing Water With the carrier liquid so that the CC goes to the Water phase.

This step S5 is illustrated as being performed in a separate unit RV”. This is notstrictly necessary, and the Washing can be performed in the same reactor RV as the previous treatments, but for easy explanation it is shown in this Way.

The Washing step S5 can itself be subdivided in a number of different Washingsteps using the same or different media (e.g. displacement Washing), such as pureWater, various concentrations of aqueous acid,or other solvents capable ofdissolving and removing the CC from the organic phase. Depending on thesequence of Washing steps and the use of selected media different qualities of thefinal product can be arrived at. The Washing media may be reused for Washing forexample after removal of the CC Which preferably is returned to the pulp mill recovery boiler.

By quality in this context We mean the level of cooking chemicals/Water in the product resulting from the process.

The result of the Washing process is a product that may or may not require further processing before it is delivered for a specified use.

To be able to use the product, in a preferred embodiment, as a feed-stock and /or supplement in a refinery process, Water has to be essentially removed.Preferably the Water concentration is below 300 ppm. Thus, if there is still Waterpresent in the lignin composition, this Water needs to be removed and in theprocess of removing the Water, schematically indicated at S6, also any residualcooking chemicals dissolved in the Water Will also be recovered and returned RQ to the pulping process.

Suitably the Water removal is achieved by a decanting procedure, by centrifugation or by evaporation.

Now some embodiments Will described in terms of alternatives for the various sub-steps in the generic process described above.

Thus, the step of removing the precipitated cooking chemicals CC after thelignin has been transferred to the organic phase in step S4, can be implemented in different ways.

One way is to use physical separation e.g. by using a sieve type device,schematically indicated by reference SD, to separate the precipitated solid material.

Another method is to employ a washing step WS, schematically indicated by thearrows/vessel in broken line contour in partition B. Here, the idea is to dissolvethe precipitated cooking chemicals by adding water or any other suitable solventand then remove the solution by e.g. decanting, centrifugation or any other suitable method.

Here it can also be benef1cial to the process when the lignin has been esterif1edto use a solvent less nucleophilic than water for example an alcohol for example methanol or ethanol..

In order to improve the washing step, the organic lignin phase can be diluted bya carrier liquid, e.g. an oil, having a lower viscosity and/ or a lower melting pointtemperature to reduce the viscosity and /or the melting point temperature of thecomposition. This dilution will for example enable an improved contact betweenthe carrier liquid and the washing liquid at the mixing step at a giventemperature and mixing shear rate because of a decreased viscosity of the lignincontaining organic phase. It would presumably enable a washing step carriedout at lower temperatures due to the decreased melting point. Furthermore, anincreased rate of separation at a given temperature is also expected due to thedecreased viscosity and increased mobility of the lignin contianing organic phase.

The washing step S5 could be implemented in different ways, as mentioned ab ove . 11 For example a column type process could be used, suitably in a counter currentmanner. Thereby, the lignin composition would be fed into a scrubber at oneend thereof and washing liquid, e.g. water, would be fed from the otherdirection. The scrubber can be provided with a plurality of inlets for differentwashing liquids having different pH and ligand/ chelating concentration, inorder to treat the CC, metal ions and electrostatically bound ions present in the lignin material.

It is also conceivable to employ an ion exchange type process for this step S5.

The input or feed-stock (LC1, LC2,....LCn) for the present process is a lignin composition that can be obtained in several different ways.

One possibility is to subject black liquor to a membrane f1ltering process, forwhich the present applicants have filed a patent application, WO2015/ 137861,the disclosure of which is hereby incorporated in its entirety. In this way a muchnarrower molecular distribution is obtained, which can be better suited for the end use in e.g. a refinery.

The process involves subjecting the lignin composition to a series of membranef1ltration steps in order to dispose of both the very high molecular fractions andthe very low molecular fractions, so as to provide a composition that is wellsuited for e.g. use in a refinery. The output from this process typically has 30- 50% lignin(aq), 1-10% cooking chemicals and the balance (40-9%) water.

Another method is a commercially available process, LignoBoost®, which is a1sosubject to patent protection, e.g. EP1794363. This process yields a compositionwith very low content of cooking chemicals. It entails a precipitation followed byan acid treatment. Thus the acid consumption in the overall process will berather high. The output from this process typically has 65% lignin(aq), <5% cooking chemicals and the balance (about 30-34%) water.

Another method simply involves precipitation and has been known for many decades, and the LignoBoost process is a development of such precipitation 12 method. The output from this process typically has 65% lignin(aq), 5-10% cooking chemicals and the balance (2 5-30%) water.

Still another method provides a liquid lignin. However, this is only achievableunder elevated pressures, and thus the process has to be integrated in a plantfor performing the method disclosed in this application. The output from this process typically has 60% lignin (aq), 10% cooking chemicals and 30% water.

The simplest method is to utilize evaporated black liquor. Evaporation of blackliquor already takes place at all pulping plants for recovery purposes, and yieldsan output product typically having 65-80% dry matter, wherein lignin(aq)accounts for about 50% (i.e. about 32-40% of the total composition), cookingchemicals accounts for about 50% (i.e. about 32-40% of the total composition), and the balance (i.e. 20-35%) water.

Thus, generally speaking the aqueous lignin composition comprises at least 30%by weight lignin, preferably at least 40, more preferred 50 % by weight lignin, lessthan 40 % by weight cooking chemicals, preferably less than 20 % by weight, most preferred between 1 and 10 % by weight, and the balance water.

Embodiments of a system for performing the various alternatives of the method disclosed above will now be given with reference to Figs. 2-4.

Thus, Fig. 2 is a process set up comprising a miXing vessel to which black liquorin an aqueous phase containing cooking chemicals and lignin is input as rawmaterial. A suitable oil, such as a gas oil or triglycerids or a fatty acid is fed intothe miXing vessel suitably under stirring, whereby two phases are obtained, anorganic phase and an aqueous phase. Some of the low molecular lignin willdissolve in the organic phase already at this point whereas most of the ligninremains in the aqueous phase. In this embodiment the two phase system istransferred to a reactor suitable as an evaporator and as an esterification reactor. 13 Thus, in a first step in this reactor Water is removed by evaporation to get rid ofmost of the Water. Cooking chemicals and the dissolved lignin Will precipitate in solid or crystalline form.

In a second step the lignin is modified for example by esterification. In oneembodiment an esterif1cation agent (e.g. an anhydride) and optionally a Catalyst(e.g. N-methyl imidazole) are added and heat is applied, in order to induce anesterification process. Thereby the lignin Will become hydrophobic and most ofthe lignin Will therefore dissolve in the organic phase, Whereas the cooking chemicals are unaffected and remains in solid, precipitated form.

Now the content of the reactor is passed through a sieve in order to separate theprecipitated cooking chemicals. The separated material is transferred back tothe pulping plant for reuse, Whereby the economy of the process is greatly improved.

The carrier liquid and lignin composition (referred to as Lignol®) is transferred to a scrubber for Washing.

The scrubber can be operated in several steps using different Washing media,suitably beginning With Water or an organic solvent, and subsequentlyincreasingly acidic media are used for Washing, such as Weakly acidic (HgCOg) in the first stages and ending With strongly acidic (H2SO4) .

In another embodiment, instead of sieving, a Washing step can be applied, seeFig. 3, Whereby the precipitated cooking chemicals are dissolved again and thenthe organic phase can be decanted off. This is schematically illustrated by showing the vessel in a tilting position.

In this embodiment it has been discovered that addition of a suitable solvent for the lignin such as an alcohol is beneficial.

The Washed lignin in organic phase is passed to a scrubber as in the previous embodiment for further purification. 14 After the Washing treatment in the scrubber or mixing any residual Waterremaining in the composition is preferably removed prior to use in e.g. a refinery.

Thus, the Washed composition is subjected to some further treatments such asevaporation, centrifuging or decanting, or a combination, schematically illustrated in Fig. 4.

Claims (13)

:

1. Process for making a purified lignin Composition comprising a Carrier liquid suitable for processing in a ref1nery, comprising providing an aqueous lignin Composition comprising lignin, Cooking Chemicals and Water;adding a Carrier liquid to the aqueous lignin to provide an organic phase,removing all or substantially all the Water from the Composition,preferably at least 90%, more preferred more than 95% of the Water, even morepreferred more than 99 % of the Water, suitably by any of heating, evaporation, osmosis, membrane filtration; processing said lignin Composition to make the lignin more soluble in the Carrier liquid in order to transfer more of the lignin to the organic phase, optionally removing Cooking Chemicals that have precipitated by physcial separation, removing Cooking Chemicals Comprises a step of Washing by liquid / liquid eXtraCtion using a Washing liquid; and removing Washing liquid.

2. Process according to Claim 1, Wherein the Washing liquid is Water.

3. Process according to Claim 1, Wherein the physical separation of any precipitated Cooking Chemicals before the Washing step is performed by sieving, filtration or centrifugation.

4. Process according to any preceding Claim, Wherein a Carrier liquid, e.g. an oil, is added under mixing to enable an improved Washing step. 16

5. Process according to any preceding claim, Wherein the processing to make ligninWater insoluble comprises esterification, etherification, hydrogenation or protonation.

6. Process according to claim 2, 3 or 4, comprising a Washing step after removingcooking chemicals, said Washing step comprising a plurality of sub-steps Withdifferent Washing media, such as Water, Weak acid, strong acid, chelating agents, ligands or other solvents Where the cooking chemicals are dissolved or removed.

7. Process according to claim 6 , further comprising separating any remainingWater and residual solids/ cooking chemicals from the Washed composition toobtain an essentially Water free lignin containing solution of lignin in an organic phase, suitably by decanting or evaporation.

8. Process according to claim 6 or 7, Wherein said Washing step comprises a liquid- liquid extraction process.

9. Process according to any preceding claim, Wherein the aqueous lignincomposition comprises at least 30% by Weight lignin, preferably at least 40, morepreferred 50 % by Weight lignin, less than 40 % by Weight cooking chemicals,preferably less than 20 % by Weight, most preferred between 1 and 10 % by Weight, and the balance Water.

10. Process according to claim 5, Wherein the process comprises esterification.

11. Process according to claim 5, Wherein the process comprises etherification.

12. Process according to any one of the preceding claims, Wherein the carrier liquid is fatty acid or esterified fatty acid.

13. Process according to any one of the preceding claims, Wherein the carrier liquid is a hydrocarbon oil.