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EP4261343A1 - Umwandlung von biomasserückständen in bioöl - Google Patents

Umwandlung von biomasserückständen in bioöl Download PDF

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Publication number
EP4261343A1
EP4261343A1 EP22168234.7A EP22168234A EP4261343A1 EP 4261343 A1 EP4261343 A1 EP 4261343A1 EP 22168234 A EP22168234 A EP 22168234A EP 4261343 A1 EP4261343 A1 EP 4261343A1
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EP
European Patent Office
Prior art keywords
lignin
bio
process stream
pulp
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP22168234.7A
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English (en)
French (fr)
Inventor
Christian Kugge
Anders EDLING HULTGREN
Milan Kolar
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SCA Forest Products AB
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SCA Forest Products AB
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Priority to EP22168234.7A priority Critical patent/EP4261343A1/de
Priority to EP23718233.2A priority patent/EP4508264A1/de
Priority to PCT/EP2023/059133 priority patent/WO2023198587A1/en
Publication of EP4261343A1 publication Critical patent/EP4261343A1/de
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes

Definitions

  • the present invention relates to the production of a lignin-containing process stream by subjecting biomass residues to a treatment under strong alkaline conditions and obtaining a lignin-containing process stream from the reactor.
  • Lignin is one of the two major components of lignocellulose in plants. Structurally it is a class of complex cross-linked phenolic polymers. From an energy point of view, lignin has a high C/O ratio and accounts for a substantial proportion of carbon-based energy in lignocellulose. In the past however, lignin has only been considered as byproduct of the pulp and paper industry. Only a minor amount of lignin produced by the pulp and paper industry was utilized commercially and the remainder was used as a low-value fuel. Recently, efforts have been made to recover lignin and convert it to bio-oil.
  • Lignin may be recovered from hardwood, softwood but also from young plants, annual plants or energy crops.
  • lignin from softwood, such as pine or spruce, or hardwood, such as birch, is used so far.
  • Softwoods have a higher content of lignin than hardwoods.
  • WO 2004/106624 A1 discloses the production of pulp and lignin from a lignocellulosic material, comprising the impregnation of a lignocellulosic material with acid and acidic depolymerization of lignin before alkaline treatment.
  • the alkaline digestion step is performed under mild conditions, i.e., at a temperature of less than 100°C.
  • WO 2020/084196 A1 discloses a process for extracting valuable components from a tannin-rich bark raw-material by carrying out an alkaline cooking step, followed by acid precipitation to separate valuable components from the remaining bark pulp. Alkaline cooking is carried out at relatively mild alkali conditions, i.e., 14-20% effective alkali charge. Depolymerization of lignin is not disclosed.
  • WO 2020/245071 A1 discloses the production of pulp for tissue products.
  • the starting material is eucalyptus bark chips which have been pre-extracted with an ethanol-water mixture.
  • the extracted bark chips are subjected to an alkali treatment at effective alkali charge of 22%.
  • the digestion time is 200 minutes or longer and the temperature from 17-170°C. Depolymerization of lignin is not disclosed.
  • An object of the present invention was to provide economically feasible methods for the production of lignin and a bio-oil comprising depolymerized lignin.
  • the present invention provides a novel process for producing a lignin-containing process stream by subjecting a biomass residue to a treatment under strong alkaline conditions and obtaining a lignin-containing process stream from the reactor.
  • the lignocellulosic biomass residue used in accordance with the present invention is generally referred to as low value lignocellulosic biomass.
  • the process may combine the use of lignocellulosic biomass residues with the depolymerization of lignin and optional production of biofuel from the depolymerized lignin.
  • a first aspect of the invention relates to a method for producing a lignin-containing process stream, comprising the steps of:
  • the lignocellulosic biomass residue may, e.g., be sawdust, bark, branches, needles, young plants and/or straw.
  • the lignocellulosic biomass residue is selected from sawdust, wood flour, wood chips, bark, branches, leaves, needles, or any mixture thereof.
  • the lignin-containing process stream obtained in step (d) or (e) is a black liquor, particularly a black liquor that does not comprise substantial amounts of solid pulp.
  • the lignin-containing process stream obtained in step (d) comprises solid pulp, particularly low-grade solid pulp, particularly wherein the pulp yield is from about 20% to about 45% based on dry feed of lignocellulosic biomass residue, and/or wherein the low-grade solid pulp has a Kappa number of about 50 or less, particularly of about 30 or less, more particularly of about 5 to about 20.
  • the invention relates to a method that ultimately allows to obtain a bio-oil composition from the lignin-containing process stream obtained in step (d) described above.
  • the lignin-containing process stream is subjected to a lignin-depolymerization step whereby a bio-oil containing process stream is obtained.
  • a bio-oil composition may be obtained wherein the bio-oil composition comprises depolymerized lignin.
  • the bio-oil composition may be subjected to further treatment steps including distillation and/or hydrotreatment.
  • the invention relates to a bio-oil composition obtained by a method or process as described herein.
  • the present invention provides a novel process for the production of a lignin-containing process stream from lignocellulosic biomass residue by subjecting it to a treatment in the presence of an alkali source at elevated temperature.
  • a lignocellulosic biomass residue such as sawdust, wood flour, bark, branches or needles from softwood and/or hardwood or any mixture thereof is provided.
  • the biomass is fed to a reactor, e.g., batch-wise or continuously.
  • the biomass is, according to step (c) of the new process, cooked in the presence of an alkaline solution, for example, white liquor, NaOH or KOH to produce a high yield lignin-containing process stream.
  • step (d) the lignin-containing process stream is obtained from the reactor.
  • a further step (e) may be performed, by which char is removed from the lignin-containing process stream obtained after step (d).
  • the lignocellulosic biomass residue can be completely liquefied in the reactor or converted to a process stream containing pulp.
  • the basics of these two approaches are described below.
  • Both approaches differ from a conventional cooking process for production of pulp.
  • the conditions are very harsh, and the focus is to recover lignin, cellulose and hemicellulose in the process stream.
  • the recovery of pulp is not crucial in the process of the invention.
  • a pulp fraction is produced, it is typically a fraction suitable for, for example, ethanol production. Such a pulp is sometimes referred to as being a low value fraction, as compared to a pulp produced by a conventional pulp manufacturing process.
  • the process stream obtained after step (d) or (e) of the new process is especially suitable for further treatment, e.g., in a depolymerization process for the production of a bio-oil.
  • the resulting process stream e.g., a black liquor
  • the resulting process stream will have higher content of lignin and extracted organic substances including converted cellulose and hemicellulose to cellulose- and hemicellulose-based derivatives (such as sugars and organic acids) when compared to a black liquor from a conventional pulping process.
  • the higher content of lignin and cellulose- and hemicellulose-based derivatives results in a higher bio-oil yield after depolymerization of lignin.
  • the increased content of cellulose- and hemicellulose-based derivatives in the black liquor has a beneficial effect on the processability of the black liquor during and/or after lignin depolymerization.
  • the novel process of the present invention utilizes lignocellulosic biomass residue material.
  • "Lignocellulosic biomass residue” as used herein relates to biomass of plant origin, e.g., from trees, bushes, weeds or grass or straw which is without or only low value for typical applications of plant-derived biomass such as manufacture of pulp and/or formed wooden parts such as furniture, panels, roofing, flooring, joinery etc.
  • the plant-derived lignocellulosic biomass residue may comprise wood residues and/or agricultural residues.
  • agricultural residues such as straw (e.g. wheat, rye, barley, oat or rice straw), bagasse, cotton stalk and bran (e.g. wheat, rye, barley, oat or rice bran) may be utilized.
  • the lignocellulosic biomass residue may be a tree-derived material, e.g., wood residue material such as sawdust, wood flour, or wood chips, bark, branches, leaves, needles, or any mixture thereof.
  • the lignocellulosic biomass residue may be derived from softwood such as fir, pine, spruce, larch, hemlock, cedar and/or yew and/or from hardwood such as oak, beech, birch, eucalyptus etc.
  • the lignocellulosic biomass residue is wood residue material such as sawdust, wood flour and wood chips without a substantial amount, e.g., 10% (w/w) or more of bark material.
  • the lignocellulosic biomass residue is a softwood residue material comprising sawdust, wood flour, bark, branches, needles, or any mixture thereof.
  • the lignocellulosic biomass residue is softwood residue material, in particular softwood residue material comprising sawdust.
  • the lignocellulosic biomass residue essentially consists of softwood sawdust.
  • "essentially consists of” means that at least about 95% (w/w), particularly about 97% (w/w), about 98% (w/w), about 99% (w/w), or even about 99.5% the lignocellulosic biomass residue is softwood sawdust. The remaining percentage to 100% (w/w) may consist of usual contaminations in sawdust known to the skilled person (such as ash and traces of bark).
  • the total biomass introduced into the reactor comprises at least about 50% (w/w), at least about 70% (w/w), or at least about 90% (w/w) of lignocellulosic biomass residue. In certain embodiments, the total biomass introduced into the reactor consists of lignocellulosic biomass residue.
  • the lignocellulosic biomass residue is introduced into the reactor without a pretreatment, e.g., a pretreatment selected from acid impregnation and/or extraction using an organic solvent, e.g., an ethanol/water mixture.
  • a pretreatment selected from acid impregnation and/or extraction using an organic solvent, e.g., an ethanol/water mixture.
  • the reactor can be any suitable reactor capable of withstanding harsh alkaline conditions and high temperature.
  • a ratio of dry feed to liquid is adjusted in the reactor.
  • liquid refers to the liquid components present in the reactor forming a reactor medium.
  • the liquid components comprise water, an alkali source and further optional components such as alcohols.
  • the alkali source typically comprises a hydroxide, for example, Ba(OH) 2 , NaOH and/or KOH.
  • the alkali source may comprise a mixture of a hydroxide and a sulfide salt. In such a case, the alkali source may be white liquor, i.e., a mixture of NaOH and Na 2 S.
  • the effective alkali charge in the reactor is adjusted to be at least about 25% on dry wood in order to provide sufficiently harsh alkaline conditions for digesting the lignocellulosic biomass residue. In certain embodiments, the effective alkali charge in the reactor is adjusted to least about 30%, particularly from about 35% to about 60% on dry wood.
  • the effective alkali charge refers to the combined concentrations of NaOH and Na 2 S (when present) as [NaOH] + 1 ⁇ 2 [Na 2 S] (g/l) and later converted to % charge as mass alkali divided by mass dry wood.
  • the treatment conditions can be adapted to the desired degree of liquefaction of the lignocellulosic biomass residue.
  • the temperature in the reactor is typically about 150°C or higher, e.g., about 150°C to about 280°C. In some embodiments, the temperature may be between about 150°C to about 200°C. In other embodiments, the temperature may be between about 170°C to about 230°C. In yet further embodiments, the temperature may be between about 200°C and about 250°C. In exemplary embodiments, the temperature may range between 175°C and 180°C, or between 200°C and 230°C. Pressures used are typically no lower than the saturation pressure of water at chosen operation temperature. Pressures further are typically such that no water is evaporated.
  • the treatment time is at least about 1 h, typically about 1 h to about 10 h, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 h. In exemplary embodiments, the treatment time may be about 1 h, about 5 h or about 6 h.
  • treatment may be performed for about 2 h at about 230°C, for about 5 h at about 155°C, for about 1.5 h at about 180°C, for about 5 h at about 200°C, for about 6 h at about 180°C, or for about 8 h at about 180°C, such as 178°C.
  • the treatment conditions may also be defined by the Kraft H factor (also simply referred to as "H factor” in the following) that combines cooking temperature and time into a single variable that indicates the extent of reaction (cf. Pratima Bajpai, in Biermann's Handbook of Pulp and Paper, Third Ed., 2018, chapter 13.6 ) the content of which is herein incorporated by reference.
  • H factor also simply referred to as "H factor” in the following
  • H ⁇ 0 t e 43.2 ⁇ 16115 T dt
  • H factor one can control the severity of the pulping process and can compare it to a kraft pulp mill, which typically operates at a much lower H factor of 1000-1400 as well as a lower alkali charge of typically 20% on dry wood.
  • the H factor particularly is at least about 2000. In certain embodiments, the H factor is at least about 4000, at least about 6000 or at least about 7000. In preferred embodiments, the H factor is at least about 8000.
  • the maximum of the H factor according to the present invention is typically 5 000 000, particularly 3 000 000. In preferred embodiments, the H factor is about 1 000 000 or below.
  • the treatment conditions are adapted such that a substantially complete liquefaction of the lignocellulosic biomass residue is achieved.
  • a resulting stream thus does not comprise a substantial amount of solid pulp.
  • the H factor is at least about 2000 and at most about 3 000 000, particularly at most about 1 000 000, at most about 500 000, or at most about 200 000.
  • the H factor is in the range of about 8000 to about 1 000 000, particularly about 9000 to about 750 000, more particularly about 10000 to about 500 000.
  • the treatment conditions are adapted such that a pulp, particularly a low-grade solid pulp, is obtained after the treatment.
  • the H factor is in the range of about 2000 to about 13000. In preferred embodiments, the H factor is in the range of about 8000 to about 12000.
  • the lignocellulosic biomass residue is subjected to treatment conditions resulting in a substantially complete liquefaction of the biomass within the reactor except in some cases for the formation of char, e.g., in a yield of about 15% or less or 10% or less based on the total amount of biomass introduced into the reactor, which can be removed from the process stream, e.g., by filtration.
  • the lignin-containing process stream obtained in step (d) is a black liquor.
  • the lignin-containing process stream obtained in step (d) does not comprise substantial amounts, e.g., about 5% (w/w) or less or about 1% (w/w) or less of solid pulp.
  • the lignin-containing process stream obtained in step (d) contains about 0.1% (w/w) or less of solid pulp.
  • Benefits with this approach of utilizing a liquefied biomass are good processability, e.g., easy pumping, no removal of pulp and a high yield of bio-oil.
  • the treatment conditions for this approach are a temperature of about 180°C or higher, particularly from about 200°C to 280°C, and more particularly from about 210°C to about 240°C, and/or a treatment time from about 1 h to about 10 h.
  • a cooking time of 6 h for example, cooking at 210°C equals an H factor of 114 000, and cooking at 240°C equals an H factor of 800 000.
  • the reactor is a stirred reactor loaded with dry sawdust powder (wood flour) using Kraft mill white liquor as an alkali source, the temperature is at least 180 °C, the liquid/dry mass ratio is about 5/1 and/or the residence time is about 5 h or more.
  • Diluted white liquor e.g., 1/1 with water or black liquor also works to liquefy the biomass, e.g., sawdust.
  • the liquid may be cooled down and filtered to remove char.
  • the cooking time is about 1 h.
  • the lignocellulosic biomass residue is softwood residue material comprising sawdust and/or bark from softwood.
  • the treatment of biomass results in a process stream, e.g., a black liquor stream, comprising solid pulp.
  • a process stream e.g., a black liquor stream
  • the pulp contains a low amount of lignin.
  • the pulp can be released from the reactor under conditions where fibers are torn apart providing a low pulp strength, e.g., by creating a "steam explosion" when exiting the reactor.
  • the low pulp strength is advantageous for certain applications, e.g., production of ethanol, while not being wanted in traditional Kraft pulping.
  • the treatment conditions for this approach are a temperature between about 180°C and about 200°C, particularly between about 165°C to about 190°C, and more particularly between about 175°C to about 180°C, and/or a treatment time from about 3 h to about 8 h.
  • the lignin-containing process stream obtained in step (d) or (e) comprises low-grade pulp with the tensile index of 60 kNm/kg.
  • the pulp yield is from about 20% to about 45% based on dry feed of lignocellulosic biomass residue.
  • the low-grade pulp has a Kappa number of about 50 or less, particularly of about 30 or less, more particularly of about 5 to about 20.
  • the pulp may be separated from the lignin-containing process stream and optionally subjected to further processing, e.g., processing to sugar, biofuel such as ethanol, and/or biochemicals such as furan dicarboxylic acid (FDCA).
  • further processing e.g., processing to sugar, biofuel such as ethanol, and/or biochemicals such as furan dicarboxylic acid (FDCA).
  • FDCA furan dicarboxylic acid
  • the lignin-containing process stream obtained in step (d) or (e) is typically a black liquor. Compared to conventional black liquor, it comprises an increased content of dissolved organic matter, as can be determined, e.g., by comparison of the lignin content in pulp obtained from a kraft mill vs. pulp obtained according to the process of the present invention.
  • the content of dissolved organic matter in the process stream of the invention is from about 60% to about 90% of dry solids content, particularly from about 65% to about 90% of dry solids content.
  • the lignin-containing process stream obtained in step (d) or (e) comprises about 30 weight-% to about 50 weight-% of lignin, preferably >33 weight-%, more preferably >40 weight-% lignin based on the dry solid content within the process stream.
  • the lignin-containing process stream obtained after step (d) or (e) is subjected to a lignin depolymerization step in a depolymerization reactor whereby a bio-oil containing process stream is obtained.
  • the bio-oil containing process stream may be subjected to further work-up and/or purification steps to obtain a bio-oil composition comprising depolymerized lignin.
  • one or more of the following steps may be performed:
  • the acidification may, in exemplary embodiments, be carried out at a pH of from about 2 to about 5.
  • the lignin-containing process stream obtained in step (d) or (e) is subjected to a lignin-depolymerization step without addition of further components.
  • the lignin-containing process stream obtained in step (d) or (e) is subjected to a lignin-depolymerization step with addition of further components, e.g., a conventional Kraft black liquor, lignin derived components and/or non-lignin derived components.
  • Lignin derived components may include solid lignin powder and/or a depolymerized and partially hydrotreated, e.g., a partly deoxygenated and partly desulfurized bio-oil.
  • Non-lignin derived components may include a fatty acid, particularly a rosin containing oil and more particularly tall oil and any product derived therefrom comprising rosin constituents, particularly resin acids, e.g., abietic acid and/or pimaric acid.
  • the rosin containing oil may be selected from crude tall oil and fractions of crude tall oil such as tall oil pitch, tall oil rosin, tall oil fatty acids, crude sulphate turpentine and/or any combination thereof.
  • the lignin depolymerization reaction is carried out in a reactor under conditions of elevated temperature and elevated pressure, which are suitable for conducting the depolymerization reaction.
  • the depolymerization reactor may be kept at a temperature between about 150°C and about 350°C, particularly between about 210°C and about 290°C, more particularly between about 230° and 250°C and/or at a pressure between about 5 bar and about 180 bar, particularly between about 15 bar and about 120 bar, optionally in the presence of a gas such as H 2 , CO or H 2 or H 2 /CO, particularly in the presence of H 2 , and optionally in the presence of a catalyst.
  • a gas such as H 2 , CO or H 2 or H 2 /CO
  • the depolymerization reactor may be the same reactor as the reactor of the alkali treatment or, alternatively, the depolymerization reactor may be a separate reactor.
  • a wide range of catalysts can be used such as a noble metal on a support such as a carbon-based support, e.g., activated carbon, charcoal, graphene, carbon nanotubes, or graphite, or a metal oxide-based support such as alumina, aluminum phosphate, zeolite, hydrotalcite, hydroxyapatite, magnesium oxide, zirconia, titanium dioxide, ceria, chromite, or molybdite.
  • a support such as a carbon-based support, e.g., activated carbon, charcoal, graphene, carbon nanotubes, or graphite
  • a metal oxide-based support such as alumina, aluminum phosphate, zeolite, hydrotalcite, hydroxyapatite, magnesium oxide, zirconia, titanium dioxide, ceria, chromite, or molybdite.
  • transition metals such as V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and W or transition metal oxides such as NiO on any of the previously mentioned supports, as well as unsupported metal, metal oxide, metal carbide or metal nitride particles wherein the metal is particularly a transition metal such as Ni or Mo, which may be doped with another transition metal.
  • transition metal oxides such as Ni or Mo, which may be doped with another transition metal.
  • unsupported catalysts that are suitable include Co-Mo-S, MoS 2 , VS 2 , Ni-Mo and Fe-Cu catalysts.
  • Suitable lignin depolymerization procedures are described in co-owned patent applications WO 2017/048163 A1 , WO 2017/048164 A1 , WO 2020/161313 A1 , WO 2020/161323 A1 , WO 2022/002774 A1 and WO 2022/002775 A1 , the contents of which are herein incorporated by reference.
  • the bio-oil containing process stream may subjected to one or more additional treatment steps, e.g., work-up and/or purification steps, for example, acidifying the bio-oil containing process stream, e.g., with an acidifying agent selected from H 2 SO 4 , CO 2 , SO 2 , acidic process water having a pH of about 1 to about 3 or any combination thereof; adding a rosin containing oil such as crude tall oil to the bio-oil containing process stream; adding a solvent suitable to at least partially dissolve lignin components, such as ethanol or methanol, to the process stream; and/or removing an aqueous phase, solvent and/or salts from the bio-oilcontaining process stream.
  • additional treatment steps e.g., work-up and/or purification steps, for example, acidifying the bio-oil containing process stream, e.g., with an acidifying agent selected from H 2 SO 4 , CO 2 , SO 2 , acidic process water having a pH of about
  • the added solvent has two functions, being a solvent for the lignin and an anti-solvent for the salts.
  • ethanol or methanol is used to achieve the advantageous double function as lignin solvent and salt anti-solvent.
  • Other examples are ethylene glycol, diethylene glycol, glycerol or benzyl alcohol or lignin derived monomeric or oligomeric phenolics.
  • the anti-solvent function results in an improved salt removal since no additional step, such as a precipitation step, is needed before filtration.
  • Another advantage of using e.g. ethanol or methanol is that it enables the use of a lower pH, such as pH ⁇ 4.5, without problems with lignin aggregates ("lumps").
  • a bio-oil composition As a product from the work-up and/or purification steps, a bio-oil composition can be obtained.
  • the bio-oil composition comprises depolymerized lignin and further organic components from the biomass residue.
  • the bio-oil composition includes a high content of organic components from the lignocellulosic biomass residue.
  • the molecular weight of the bio-oil (after drying) may be in the range of about 200 g/mol to about 2500 g/mol, preferably about 250 g/mol to about 2200 g/mol, more preferably about 700 g/mol to about 2000 g/mol, most preferably about 800 g/mol to about 1800 g/mol. Determination of the average molecular weight may be performed as described in the Examples. According to an elemental analysis, the bio-oil (after drying) comprises about 35 to 45 wt% C, about 4.5 to about 5.5 wt% H, about 0.1 wt% or less N and about 25 to about 32
  • an aqueous phase may be obtained.
  • the aqueous phase includes liquefied carbohydrates from the lignocellulosic biomass residue such as organic acids, sugars, sugar derivatives and humins. These can be isolated in a separate process, e.g., using anti-solvent, ultrafiltration, nanofiltration or by non-selective water evaporation giving a carbohydrate rich oil or syrup.
  • the bio-oil composition is further subjected to distillation and/or hydrotreatment.
  • biofuels may be produced in a high yield from lignocellulosic biomass residues.
  • Hydrotreatment may, e.g., involve a treatment in the presence of a reducing gas such as H 2 and/or CO and a hydrotreatment catalyst at an elevated temperature, e.g., at a temperature between about 220°C to about 400°C, particularly between about 270°C and about 350°C.
  • the product resulting from the hydrotreatment may be a hydrocarbon product containing only minor amounts of nitrogen, sulfur and/or oxygen.
  • the invention also relates to a lignin containing process stream obtainable by a process as described herein.
  • the lignin containing process stream according to the invention contains all turpentine and all methanol and all tall oil which is later part of the final bio-oil.
  • the kraft mill black liquor used in the prior art does not contain any or at most traces of tall oil, turpentine and methanol. The reason for this is that turpentine and methanol are removed within the digester/cooker and the tall oil is skimmed off as tall oil soap. The resulting lean black liquor goes to the evaporators.
  • the tall oil and turpentine are also called extractives and the total amount of extractives usually are 2-5% of dry wood, e.g. 2% for spruce and 5% for pine.
  • the invention also relates to a bio-oil composition obtainable by a process as described herein.
  • an oven dry bio-oil composition according to the invention has a melting point, whereas a commercial oven dry lignin powder does not.
  • the bio-oil composition according to the invention contains more cellulose/hemicellulose-based derivatives.
  • the bio-oil composition according to the invention contains all tall oil and all turpentine and all methanol available, whereas the lignin oil of the prior art does not contain tall oil, turpentine and methanol.
  • the melting point of the bio-oil composition according to the invention may lie in the range of about 120°C to about 180°C (at normal pressure), particularly in the range of about 130°C to about 170°C.
  • the oil melting point may be about 130°C.
  • the bio-oil composition according to the invention will also contain salts, including, but not limited to sodium sulfate and/or sodium carbonate.
  • the salt content may range, e.g., between about 15% (w/v) to about 20% (w/v).
  • the bio-oil composition contains 15-20% salt as all salt is not removed with filtration.
  • Lignin-oil according to the prior art contains only about 50 ppm salts.
  • the pH of black liquor produced was 13.9.
  • the black liquor was acidified to pH 4.5 to protonate the lignin.
  • the black liquor was extracted with the solvent ethyl acetate to separate any depolymerized lignin oil (bio-oil). This gave almost no product which indicates the need for a further depolymerization step with higher temperatures, e.g., 230-300°C.
  • the black liquor was heated for 2 h at 230°C in a second step to depolymerize the lignin within the black liquor.
  • Sulfuric acid (12.8 g) was used to acidify the 77.7 g heat treated black liquor to reach pH 4.5.
  • the acid consumption was 165 kg/ton black liquor.
  • Ethyl acetate 500 g was added to extract the depolymerized lignin oil (bio-oil) by phase separation.
  • the dry weight of bio-oil was 1.95 g. As the lignin content of softwood is 27% this gave a bio-oil yield of 77% based on the lignin content and a yield of 21% based on total dry biomass.
  • Char was filtrated off and the liquefied bark (pH 13.9) was acidified to pH 3 with 1:1 mass ratio of ethanol present.
  • the precipitated sodium sulfate was filtered off. Salt recovery was 88% based on added sulfuric acid.
  • the filtrate contained most organics from the liquefied bark as the precipitated salt only contained 1.2% organics.
  • the filtrate was dried to obtain dry bio-oil.
  • the weight of dry bio-oil was 8.0 g including 26% ash.
  • the dry bio-oil yield based on dry ash-free bark was 68%.
  • pilot cooking examples 2.1-2.5 are also summarized together with data from further examples in the table below.
  • reference 1 corresponds to example 2.1 and so on.
  • the black liquor was heat treated for 1 h at 230°C.
  • Sulfuric acid was added to the lignin containing liquor to reach pH 5 followed by adding ethanol in 1:1 mass ratio.
  • the produced slurry was filtered to remove sodium sulfate.
  • the sodium sulfate recovery was 85% based on added acid and it contained 5% organics.
  • the filtrate was dried to obtain 24.5 g dry oil including 27% ash.
  • Molecular weight of the lignin containing bio-oil was analyzed to be 1480 Da using the method of dissolving the bio-oil in sodium hydroxide. Dry bio-oil started to melt at 130°C using the method of heating the bio-oil on a glass plate and detecting the melting point with an IR thermometer.
  • the black liquor was heat treated for 1 h at 230°C.
  • Sulfuric acid was added to the lignin containing liquor to reach pH 5 followed by adding ethanol in 1:1 mass ratio.
  • the produced slurry was filtered to remove sodium sulfate.
  • the sodium sulfate recovery was 57% based on added acid and it contained 6% organics.
  • the filtrate was dried to obtain 31.4 g dry oil including 30% ash. Dry bio-oil started to melt at 140°C using the method of heating the bio-oil on a glass plate and detecting the melting point with an IR thermometer.
  • the black liquor was heat treated for 1 h at 230 °C.
  • Sulfuric acid was added to the lignin containing liquor to reach pH 5 followed by adding ethanol in 1:1 mass ratio.
  • the produced slurry was filtered to remove potassium sulfate.
  • the potassium sulfate recovery was 95% based on added acid and it contained 10% organics.
  • the filtrate was dried to obtain 24.7 g dry oil including 26% ash.
  • Molecular weight of the lignin containing bio-oil was analyzed to be 1740 Da using the method of dissolving the bio-oil in sodium hydroxide. Dry bio-oil started to melt at 170 °C using the method of heating the bio-oil on a glass plate and detecting the melting point with an IR thermometer.
  • the black liquor was heat treated for 2 h at 230 °C.
  • Sulfuric acid was added to the lignin containing liquor to reach pH 5 followed by adding ethanol in 1:1 mass ratio.
  • the produced slurry was filtered to remove potassium sulfate.
  • the potassium sulfate recovery was 95% based on added acid and it contained 11% organics.
  • the filtrate was dried to obtain 25.0 g dry oil including 23% ash.
  • Molecular weight of the lignin containing bio-oil was analyzed to be 1730 Da using the method of dissolving the bio-oil in sodium hydroxide. Dry bio-oil started to melt at 125 °C using the method of heating the bio-oil on a glass plate and detecting the melting point with an IR thermometer.
  • Table 1 summarize the pilot cooker trials and contain results from further pilot cooker trials. Reference no. 1 in the table below refers to pilot cooker trial example 2.1 and so on. Reference nos. 6-14 relate to examples, which are not described above in detail. Table 1: Ref. Batch Feed Dry feed (kg) Liquid volume (I) Cooking time (min) Cooking temperature (°C) H-factor Alkali source Effective alkali charge (%) Residual alkali (g/l) Pulp yield (%) Kappa number Lignin in pulp (%) 1 4878 Sawdust 1.5 7.5 360 178 9900 White liquor 30% 10.3 33 8.1 1.2 2 4879 Sawdust 1.5 7.5 480 178 13433 NaOH 45% 25.5 23 5.6 0.9 3 4880 Sawdust 1,5 7.5 90 178 2494 NaOH 25% 15.2 50 47.7 7.4 4 4881 Sawdust 1,5 7.5 360 178 10835 KOH 50% 10.3 35 12.5 1.9 5 4882 Bark 1,5 7.5 360 178 10264 KOH 59% 9.9 33 - 16 6
  • Table 2 summarizes and compares data for producing a lignin containing process stream and Table 3 for the work-up after a depolymerization step. The abbreviations are explained and connected to examples below. Table 2: Trial Alkali / kg dry biomass (mol) Alkali / dry biomass (wt%) Pulp yield (wt%) Temp.
  • the lower pulp yield provided by the harsher cooking conditions results in an increased amount of organic matter within the black liquor and later within the bio-oil as essentially all organics (even water-soluble compounds and the extractives) end up within the bio-oil. This particularly applies when a solvent, e.g., ethanol, is added before or during acidification.
  • a solvent e.g., ethanol
  • the molecular weight of the produced bio-oils after a depolymerization step is significantly lower than conventional lignin powder from a Kraft mill having molecular weights in order of 4000-5000 Da. Using white liquor is more efficient to depolymerize the bio-oil giving a lower molecular weight compared with KOH media.
  • the produced bio-oils have a melting point in an open atmosphere, which is different to conventional lignin powder from a Kraft mill. A melted oil is easier to process further.
  • Table 4 shows elemental analysis results of dry oils. Table 4: Trial C (%) H (%) N (%) S (%) O (%) S/WL 39 4.8 0 2.0 27 S/NaOH_s - - - - - S/NaOH_w 38 5.0 0 0 27 S/KOH_s 38 4.8 0 0.8 30.6 B/KOH_w 43 5.3 0.1 0 28.3
  • the results support the presence of increased amounts of organic matter derived from cellulose and hemicellulose within the final bio-oil.
  • the oxygen content (calculated by difference) is high compared to oil obtained from Kraft mill black liquor (25% oxygen) which indicates more oxygen-containing organic components within the bio-oil.
  • the black liquor according to the invention shows a more gold-brown color which reflects the color of tall oil, turpentine and cellulose/hemicellulose-based derivatives, whereas the kraft mill black liquor ( Fig. 2B ) is black. Liquid samples to dry were extracted from bulk black liquor and not from the surface.

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EP22168234.7A 2022-04-13 2022-04-13 Umwandlung von biomasserückständen in bioöl Withdrawn EP4261343A1 (de)

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PCT/EP2023/059133 WO2023198587A1 (en) 2022-04-13 2023-04-06 Conversion of biomass residues into bio-oil

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WO2004106624A1 (en) 2003-06-03 2004-12-09 Pacific Pulp Resources Inc. Method for producing pulp and lignin
WO2013166469A2 (en) * 2012-05-03 2013-11-07 Virdia Ltd Methods for treating lignocellulosic materials
WO2017048163A1 (en) 2015-09-16 2017-03-23 Sca Forest Products Ab A continuous process for producing bio-oil from spent black liquor
WO2017048164A1 (en) 2015-09-16 2017-03-23 Sca Forest Products Ab A batch process for producing bio-oil from spent black liquor
WO2017078582A1 (en) 2015-11-04 2017-05-11 Sca Forest Products Ab A process for producing a hydrocarbon product from lignin oil
WO2017203329A1 (en) * 2016-05-27 2017-11-30 Fibratech Pte. Ltd A method and a system for production of high molecular weight lignin
WO2020084196A1 (en) 2018-10-23 2020-04-30 Teknologian Tutkimuskeskus Vtt Oy Extraction of valuable components from bark
WO2020161320A1 (en) 2019-02-08 2020-08-13 Sca Forest Products Ab Process for the production of a hydrocarbon product
WO2020161323A1 (en) 2019-02-08 2020-08-13 Sca Forest Products Ab Process for the production of a bio-oil
WO2020161313A1 (en) 2019-02-08 2020-08-13 Sca Forest Products Ab Process for the production of a bio-oil using a rosin-containing oil
WO2020245071A1 (en) 2019-06-03 2020-12-10 Raiz - Instituto De Investigação Da Floresta E Papel Eucalyptus globulus bark pulp for tissue products
WO2022002775A1 (en) 2020-06-29 2022-01-06 Sca Forest Products Ab Production of lignin oil with an organic solvent
WO2022002774A1 (en) 2020-06-29 2022-01-06 Sca Forest Products Ab Lignin oil from young plants

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US3762989A (en) * 1971-07-30 1973-10-02 St Regis Paper Co Pyrolysis of spent pulping liquors
WO2004106624A1 (en) 2003-06-03 2004-12-09 Pacific Pulp Resources Inc. Method for producing pulp and lignin
WO2013166469A2 (en) * 2012-05-03 2013-11-07 Virdia Ltd Methods for treating lignocellulosic materials
WO2017048163A1 (en) 2015-09-16 2017-03-23 Sca Forest Products Ab A continuous process for producing bio-oil from spent black liquor
WO2017048164A1 (en) 2015-09-16 2017-03-23 Sca Forest Products Ab A batch process for producing bio-oil from spent black liquor
WO2017078582A1 (en) 2015-11-04 2017-05-11 Sca Forest Products Ab A process for producing a hydrocarbon product from lignin oil
WO2017203329A1 (en) * 2016-05-27 2017-11-30 Fibratech Pte. Ltd A method and a system for production of high molecular weight lignin
WO2020084196A1 (en) 2018-10-23 2020-04-30 Teknologian Tutkimuskeskus Vtt Oy Extraction of valuable components from bark
WO2020161320A1 (en) 2019-02-08 2020-08-13 Sca Forest Products Ab Process for the production of a hydrocarbon product
WO2020161323A1 (en) 2019-02-08 2020-08-13 Sca Forest Products Ab Process for the production of a bio-oil
WO2020161313A1 (en) 2019-02-08 2020-08-13 Sca Forest Products Ab Process for the production of a bio-oil using a rosin-containing oil
WO2020245071A1 (en) 2019-06-03 2020-12-10 Raiz - Instituto De Investigação Da Floresta E Papel Eucalyptus globulus bark pulp for tissue products
WO2022002775A1 (en) 2020-06-29 2022-01-06 Sca Forest Products Ab Production of lignin oil with an organic solvent
WO2022002774A1 (en) 2020-06-29 2022-01-06 Sca Forest Products Ab Lignin oil from young plants

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