METHODS FOR PREPARING THERMALLY STABLE LIGNIN FRACTIONS

专利摘要:
METHODS FOR PREPARING THERMALLY STABLE LIGNIN FRACTIONS The invention relates to high-purity lignin fractions that are thermally stable, and to methods of producing said fractions from lignocellulose material.
公开号:BR112015027743B1
申请号:R112015027743-8
申请日:2014-05-02
公开日:2020-06-23
发明作者:Noa Lapidot；Lapidot Noa；Robert Jansen；Jansen Robert；James Alan Lawson；Alan Lawson James；Bassem Hallac；Hallac Bassem；Rotem PERRY；Perry Rotem
申请人:Virdia, Inc.；
IPC主号:

专利说明:

[0001] Cross Reference
[0002] This claim claims benefit under Article 35 USC § 119 (e) of North American Provisional Application No. 61 / 819.485, filed on May 3, 2013 and North American Provisional Application No. 61 / 953,572, deposited on March 14, 2014, each incorporated herein by reference in its entirety. [0003] Incorporation by Reference
[0004] All publications, patents, and patent applications mentioned in that specification are hereby incorporated by reference to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference. [0005] Field of the Invention
[0006] The invention relates to a method for fractionating lignin, to stable lignin fractions, and the use of these. [0007] History of the Technique
[0008] Lignin, a highly abundant natural polymer that can be extracted from biomass, is a polymer of choice for various applications and as a chemical raw material that replaces petrochemicals. The industrial use of lignin is difficult due to its variable nature, functionality, reactivity, and heterogeneity. It is desirable to fractionate lignin into stable fractions that have reduced variability in size, composition and reactivity. The fractionation of lignin by membrane filtration using ultrafiltration and nanofiltration membranes results in unstable fractions of lignin that change while being fractionated, and is therefore sterile. It is also a challenge to characterize the fractions obtained by a reliable method, since the lignin chromatography by size is notoriously dependent on the experimental procedure and lacks good standards and adequate detectors, and must be considered as relative rather than absolute.
[0009] It is the purpose of this invention to prepare thermally stable fractions of high purity lignin by methods that can be used by industrial means. [0010] Summary of the Invention
[0011] The invention provides a method of fractionating high purity lignin into fractions that are stable. The invention further provides a way to assess the stability of lignin fractions by methods that are typically employed for synthetic polymers of much more uniform structure. The invention further provides an entire process for extracting high-purity lignin from biomass and for fractioning it into stable and distinctly different high-purity lignin fractions.
[0012] The invention also provides a lignin composition that has a stable glass transition temperature determined using differential scanning calorimetry according to DIN 53765-1994. In some embodiments, the temperature difference between the first glass cycle transition and the second glass cycle transition is less than 5 ° C.
[0013] The invention further provides a method of producing high purity lignin from biomass. The method involves (i) removing hemicellulose sugars from biomass thereby obtaining a lignin-containing remnant; wherein the remainder containing lignin comprises lignin and cellulose; (ii) placing the lignin-containing remnant in contact with a lignin extraction solution to produce a lignin extract and a cellulose remnant; wherein the lignin extraction solution comprises a limited solubility solvent, an organic acid, and water, where the limited solubility solvent and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulose remnant; wherein the lignin extract comprises lignin dissolved in the solvent of limited solubility. Optionally, the removal of hemicellulose sugars does not remove a substantial amount of cellulosic sugars. Optionally, the limited solubility solvent and the water in the lignin extraction solution are in a ratio of about 1: 1. In some embodiments, the method still involves purifying the remaining cellulose to obtain cellulose pulp. Optionally, the cellulose pulp comprises lignin in an amount of up to 10% by weight / weight. Optionally, the cellulose pulp comprises lignin in an amount of up to 7% by weight / weight. In some embodiments, the method still involves putting the lignin extract in contact with a strong acid cation exchanger to remove residual cations thereby obtaining a purified lignin extract. In some embodiments, the method also involves separating the limited solubility solvent from the lignin extract thereby obtaining high-purity lignin. In some embodiments, the method still involves evaporating the solvent of limited solubility from the lignin. Optionally, evaporation comprises spray drying.
[0014] A lignin composition characterized (based on a dry matter) by at least one characteristic selected from the group consisting of: i) a glass transition temperature (Tg) above 160 ° C or below 90 ° C as determined using differential scanning calorimetry (DSC) according to DIN 53765-1994; ii) a consistent glass transition temperature (Tg) as determined by multiple differential digitization (DSC) calorimetry runs of the same part of lignin; iii) a mass average molar mass (Mw) greater than 10,000 Da as measured by gel permeation chromatography (GPC); iv) a numerical mean (MN) molar mass greater than 6,200 Da as measured by gel permeation chromatography (GPC); v) a mass average molar mass (Mw) less than 2,500 Da as measured by gel permeation chromatography (GPC); vi) average number (MN) molar mass less than 1,000 Da as measured by gel permeation chromatography (GPC); vii) a polydispersity less than 7.00 as measured by gel permeation chromatography (GPC); viii) a CgHxOy formula; where X is less than 12 and Y is less than 3.5; ix) degree of condensation less than 0.8 as determined by NMR; x) methoxy content (# / aryl group) as determined by NMR is less than 1.4; xi) aliphatic bonds ([3-0-4 ') (# / aryl group) less than 0.6; xii) aromatic C-0 ratio: aromatic C-C: aromatic C-H (# / aryl group) 1.6: 2.3: 2.1 or 1.6: 2.2: 2.2; xiii) amount of aromatic c-o bonds (# / aryl group) is less than 2.1; xiv) elementary composition greater than 61% carbon, less than 27% oxygen, and less than 0.5% nitrogen by mass as measured by elementary analysis; xv) a solid lignin composition comprising a marker molecule in a concentration of at least 100 ppb; xvi) less than 0.1 times the volatile sulfur compounds found in kraft lignin; xvii) an ash content of less than 0.5%; xviii) an ash content of less than 0.1%; xix) a sulfur content of less than 700 PPM; xx) a phosphorus content of less than 100 PPM; xxi) a soluble carbohydrate content of less than 0.5%; xxii) substantially soluble in an organic solvent; and xxiii) substantially soluble in an organic solvent. In some embodiments, lignin is characterized in at least three of said characteristics from said group. In some modalities, lignin is characterized in at least five of the said characteristics from the group. In some modalities, lignin is characterized in at least eight of the said characteristics from the group. In some modalities, lignin is characterized in at least ten of the said characteristics from the group. In some modalities, lignin is characterized in at least twelve of the said characteristics from the group. In some modalities, lignin is characterized in at least fourteen of the said characteristics from the group. In some modalities, lignin is characterized in at least sixteen of the said characteristics from the group. In some modalities, lignin is characterized in at least eighteen of the said characteristics from the group. In some modalities, lignin is characterized in at least nineteen of the said characteristics from the group. In some embodiments, lignin is characterized (based on dry matter) by sixteen or more characteristics selected from the group consisting of: i) a glass transition temperature (Tg) above 160 ° C as determined using calorimetry differential scanning (DSC) according to DIN 53765- 1994; ii) a consistent glass transition temperature (Tg) as determined by multiple differential digitization (DSC) calorimetry runs of the same part of lignin; iii) a mass average molar mass (Mw) greater than 10,000 Da as measured by gel permeation chromatography (GPC); iv) a numerical mean (MN) molar mass greater than 6,200 Da as measured by gel permeation chromatography (GPC); v) a polydispersity less than 7.00 as measured by gel permeation chromatography (GPC); vi) a CgHxOy formula; where X is less than 12 and Y is less than 3.5; vii) degree of condensation less than 0.8 as determined by NMR; viii) methoxy content (# / aryl group) as determined by NMR is less than 1.4; ix) aliphatic bonds (3-0-4 ') (# / aryl group) less than 0.6; x) aromatic C-0 ratio: aromatic C-C: aromatic C-H (# / aryl group) 1.6: 2.2: 2.2; xi) amount of aromatic c-o bonds (# / aryl group) is less than 2.1; xii) elemental composition greater than 61% carbon, less than 27% oxygen, and less than 0.5% nitrogen by mass as measured by elementary analysis; xiii) a solid lignin composition comprising a marker molecule at a concentration of at least 100 ppb; xiv) less than 0.1 times the volatile sulfur compounds found in Lignin kraft; xv) an ash content of less than 0.5%; xvi) a sulfur content less than 700 PPM; xvii) a phosphorus content of less than 100 PPM; xviii) a soluble carbohydrate content of less than 0.5%; xix) substantially insoluble in an organic solvent. In some embodiments, lignin is characterized (based on a dry matter) by sixteen or more characteristics selected from the group consisting of: i) a glass transition temperature (Tg) below 90 ° C as determined using calorimetry differential scanning (DSC) according to DIN 53765- 1994; ii) a consistent glass transition temperature (Tg) as determined by multiple differential digitization (DSC) calorimetry runs of the same part of lignin; iii) a mass average molar mass (Mw) less than 2,500 Da as measured by gel permeation chromatography (GPC); iv) a numerical average (MN) molar mass less than 1,000 Da as measured by gel permeation chromatography (GPC); v) a polydispersity less than 7.00 as measured by gel permeation chromatography (GPC); vi) a CgHxOy formula; where X is less than 12 and Y is less than 3.5; vii) degree of condensation less than 0.8 as determined by NMR; viii) methoxy content (# / aryl group) as determined by NMR is less than 1.4; ix) aliphatic bonds (p-O-4 ') (# / aryl group) less than 0.6; x) ratio of aromatic C-0: aromatic C-C: aromatic C-H (# / aryl group) 1.6: 2.2: 2.2; xi) amount of aromatic c-o bonds (# / aryl group) is less than 2.1; xii) elemental composition greater than 61% carbon, less than 27% oxygen, and less than 0.5% nitrogen by mass as measured by elementary analysis; xiii) a solid lignin composition comprising a marker molecule at a concentration of at least 100 ppb; xiv) less than 0.1 times the volatile sulfur compounds found in Lignin kraft; xv) an ash content of less than 0.5%; xvi) a sulfur content less than 700 PPM; xvii) a phosphorus content of less than 100 PPM; xviii) a soluble carbohydrate content of less than 0.5%; xix) substantially soluble in an organic solvent. In some embodiments of the lignin described here, the lignin has a glass transition temperature above 160 ° C determined using differential scanning calorimetry according to DIN 53765-1994. In some embodiments of the lignin described here, the lignin has a glass transition temperature above 190 ° C determined using differential scanning calorimetry according to DIN 53765-1994. In some embodiments of the lignin described here, lignin has an average molar mass (Mw) greater than 10,000 Da as measured by gel permeation chromatography (GPC); and a numerical mean (MN) molar mass greater than 6,200 Da as measured by gel permeation chromatography (GPC). In some embodiments of the lignin described here, the lignin has a glass transition temperature below 100 ° C determined using differential scanning calorimetry according to DIN 53765-1994. In some embodiments of the lignin described here, the lignin has a glass transition temperature below 90 ° C determined using differential scanning calorimetry according to DIN 53765-1994. In some embodiments of the lignin described here, lignin has an average molar mass (Mw) of less than 2,500 Da as measured by gel permeation chromatography (GPC); and a numerical mean (MN) molar mass less than 1,000 Da as measured by gel permeation chromatography (GPC). In some embodiments of the lignin described here, the consistent glass transition temperature (Tg) is determined by two consecutive differential scanning calorimetry (DSC) runs of the same part of lignin according to DIN 53765-1994, in which a first Tg is measured during the first DSC run, a second Tg is measured during the second DSC run, and the difference between the first Tg and the second Tg is less than 10 ° C. In some embodiments of the compositions described here, the difference between the first Tg and the second Tg is less than 5 ° C.
[0015] In some embodiments of the lignin compositions described here, lignin is substantially soluble when a first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and a third amount of insoluble lignin, where the ratio of the second amount to the third amount of lignin is greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6 , 1,7, 1,8, 1,9, 2,0, 2,2, 2,4, 2,6, 3, 4, 5, 6, 7, 8, 9, 10, or 20 to 1 ( weight / weight), and where the ratio of the amount of organic solvent to the first amount of lignin is 5: 1 (weight / weight).
[0016] In some embodiments of the lignin compositions described here, lignin is substantially soluble when a first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and a third amount of insoluble lignin, in which more than 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50% of the first amount of lignin is dissolved in the organic solvent, and in which the ratio of the amount of organic solvent for the first amount of lignin is 5: 1 (weight / weight).
[0017] In some embodiments of the lignin compositions described here, lignin is substantially insoluble when a first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and a third amount of insoluble lignin, where the ratio of the third amount to the second amount of lignin is greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6 , 1,7, 1,8, 1,9, 2,0, 2,2, 2,4, 2,6, 3, 4, 5, 6, 7, 8, 9, 10, or 20 to 1 ( weight / weight), and where the ratio of the amount of organic solvent to the first amount of lignin is 5: 1 (weight / weight).
[0018] In some embodiments of the lignin compositions described here, lignin is substantially insoluble when a first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and a third amount of insoluble lignin, in which more than 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50% of the first amount of lignin is not dissolved in the organic solvent, and in which the ratio of amount of organic solvent for the first amount of lignin is 5: 1 (weight / weight).
[0019] In some embodiments the marker molecule is selected from the group consisting of isopropanol, ethyl acetate, ethyl formate, dichloromethane, hexanol, furfural, furfural hydroxymethyl, 2,3,5 trimethyl furan, p- hydroxyphenoxyacetic, 4-hydroxy-3,5, -dimethoxyphenyl) acetic acid, methyl ethyl ketone, methyl propenyl ketone, 3- (2-furyl) -3-penten-2-one, 3-methyl-2-penten-4- one, 3,4-dimethyl-4-hexene-one, 5-ethyl-5-hexene-3-one, 5-methyl-4-heptene ~ 3-one, o-hydroxyanisole, 3-ethyl-4-methyl- 3-penten-2-one, 3,4,4-trimethyl-2-cyclohexene-1-one, 2'-hydroxy-4 ', 5'-dimethylacetophenone, methanol 1- (4-hydroxy-3-methoxyphenyl) propane , galcturonic acid, dehydroabietic acid, glycerol, fatty acids and resin acids.
[0020] In some embodiments, the organic solvent is selected from a group consisting of methanol, ethanol, isopropanol, ethyl acetate, ethyl formate, dichloromethane and any mixture of these. There is also provided a composition comprising up to 50, 40, 30, 20, 10, 5, or 1% by weight / weight of at least one of the lignin compositions described herein. In some embodiments, the composition is a polymer, precursor to one or more chemicals, a chemical, or consumer goods. In some embodiments, the composition is selected from the group consisting of fuel additives in gasoline or diesel fuel, carbon fiber, materials for the production of carbon fiber, asphalt, a component of a biopolymer, drilling well additives from oil, concrete additives, dye dispersants, agricultural chemicals, animal feed, industrial binders, specialty polymers for the paper industry, aid for precious metal recovery, wood preservative materials, sulfur-free lignin products, brakes automotive, wood panel products, biodispersants, polyurethane foams, epoxy resins, printed circuit boards, emulsifiers, sequestering agents, water treatment formulations, power additives for paintings, adhesives, and a material for the production of vanillin , xylitol, paracoumaril, coniferyl, synaphyl alcohol, benzene, xylenes, or toluene.
[0021] In another aspect, the invention is a method for fractionating lignin which comprises: i) placing a sample comprising solid lignin in contact with an organic solvent to form a resulting biphasic mixture, wherein the mixture comprises: a) a solid remainder designated as fraction of insoluble solvent (si) comprising a first fraction of lignin; and b) a liquid solution comprising the solvent and a second fraction of the lignin, wherein the second fraction is referred to as the fraction of soluble lignin (ss) of solvent; and ii) spatially separating a fraction of lignin (si) from the fraction of lignin (ss);
[0022] in which the first fraction of lignin and the second fraction of lignin have different glass transition temperatures.
[0023] A method is also provided for producing high purity lignin from biomass, which comprises: (i) removing hemicellulose sugars from biomass thereby obtaining a remainder containing lignin; wherein the remainder containing lignin comprises lignin and cellulose; (ii) placing the remainder containing lignin in contact with the lignin extraction solution to produce a lignin extract and a cellulose remainder; wherein the lignin extraction solution comprises a limited solubility solvent, an organic acid, and water, where the limited solubility solvent and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulose remnant; wherein the lignin extract comprises lignin dissolved in the solvent of limited solubility; and although it comprises one, two, three or four additional step (s): (iv) distill or quickly evaporate the lignin extract to thereby remove most of the solvent of limited solubility from the extract of lignin to obtain a solid lignin; (v) heating the solid lignin to thereby remove solvent with a trace of limited solubility or water from the solid lignin; (vi) applying a vacuum to a solid lignin to thereby remove solvent with a trace of limited solubility or water from the solid lignin; and (vii) placing a sample comprising solid lignin in contact with an organic solvent to form a resulting biphasic mixture, wherein the mixture comprises: a) a remaining solid designated as the insoluble solvent fraction (si) comprising a first fraction of the lignin; and b) a liquid solution comprising the solvent and a second fraction of the lignin, wherein a second fraction is referred to as the fraction of soluble lignin (ss) of solvent; and ii) spatially separating the lignin fraction (si) from the lignin fraction (ss); wherein the first fraction of lignin and the second fraction of lignin have different glass transition temperatures. In some embodiments of the methods disclosed herein, the solvent comprises at least one organic molecule that has up to 5 carbon atoms and at least one heteroatom; where contact occurs at 20 to 50 ° C for 1 to 10 hours; wherein the spatial separation comprises filtration or decanting of the solvent from insoluble lignin; and the method further comprises: (iii) evaporating the solvent from the lignin fraction (ss); and (iv) drying each fraction to obtain a fraction of dry solid lignin (ss) and a fraction of dry solid lignin (SI); wherein the two fractions of dry solid lignin have different molecular weights as determined by GPC and different consistent glass transition temperatures.
[0024] In some modalities of the methods disclosed here, at least one of the lignin fractions has a consistent glass transition temperature (Tg) as determined by two differential scanning calorimetry (DSC) runs of the same part of lignin in a single day according to DIN 537 65-1994, where the first Tg is measured during the first DSC run, a second Tg is measured during the second DSC run, and the difference between the first Tg and the second Tg is less than than 5 ° C. In some embodiments, the lignin fraction (ss) has a consistent glass transition temperature different from the lignin fraction (SI). In some embodiments, the solvent is selected from a group consisting of methanol, ethanol, isopropanol, ethyl acetate, ethyl formate, dichloromethane, and any mixture of these.
[0025] A method is also provided which comprises: (i) providing a lignin composition described herein, and (ii) converting at least a part of lignin in the composition to a conversion product. In some embodiments, the conversion involves treating with hydrogen or with a hydrogen donor. In some embodiments, the conversion product comprises a chemical product comprising at least one item selected from the group consisting of bio-oil, carboxylic acid and fatty acids, dicarboxylic acids, hydroxyl carboxylic acids, hydroxyl di-carboxylic acids and hydroxyl, methylglyoxal, mono-, di- or poly-alcohols, alkanes, alkenes, aromatics, aldehydes, ketones, esters, phenols, benzene, toluenes, and xylenes fatty acids. In some embodiments, the conversion product is selected from the group consisting of dispersants, emulsifiers, complexers, flocculants, binders, pelletizing additives, resins, carbon fibers, active carbon, antioxidants, liquid fuel, aromatic chemicals, vanillin, adhesives , binders, absorbents, toxin binders, foams, coatings, films, rubbers and elastomers, sequestering agents, fuels, and expanders. In some embodiments, the conversion product comprises a fuel or a combustible ingredient. [0026] Description of the Figures
[0027] Figure 1 is a schematic representation of an exemplary method of treating lignocellulose biomass material according to some embodiments of the present invention.
[0028] Figure 2 is a schematic description of a process for extracting acidic lignin solvent from hemicellulose-depleted lignocellulose matter and for refining soluble solvent lignin. This process results in flow 200, which comprises the solvent and dissolved lignin, where residual ash is less than 1000 ppm, preferably less than 500 ppm, where polyvalent cations are less than 500 ppm, preferably less than 200 ppm in lignin (on a dry basis) and residual carbohydrate is less than 500 ppm compared to lignin (on a dry basis). The solution has no suspended particles.
[0029] Figure 3 is a gel permeation chromatography (GPC) overlay of unfractionated high purity lignin made from bagasse (NL), and its fractions obtained by methanol fractionation: SS is the soluble fraction of methanol, SI is the insoluble fraction of methanol.
[0030] Figure 4 is an overlay of unprocessed high purity lignin GPC made from bagasse (NL), and its fractions obtained by dichloromethane fractionation: SS is the soluble fraction of dichloromethane, SI is an insoluble fraction of dichloromethane .
[0031] Figure 5 is a GPC overlay of unfractionated high-purity lignin made from bagasse (NL), and its fractions obtained by ethyl acetate fractionation: SS is the soluble fraction of ethyl acetate, SI is the fraction insoluble ethyl acetate.
[0032] Figure 6A is a differential scanning calorimeter (DSC) thermogram of an unfractionated lignin (NF); Figure 6B is a DSC thermogram of methanol fraction of soluble lignin (ss) solvent; Figure 6C is a DSC thermogram of methanol solvent insoluble lignin (SI) fraction.
[0033] Figure 7A is a differential scanning calorimeter (DSC) thermogram of fraction of soluble bagasse lignin (SS) of dichloromethanol solvent; Figure 7B is a DSC thermogram of insoluble bagasse lignin (SI) fraction of dichloromethane solvent.
[0034] Figure 8A is a differential scanning calorimeter (DSC) thermogram of fraction of soluble bagasse lignin (SS) of ethyl acetate solvent; Figure 8B is a DSC Thermogram of insoluble bagasse lignin (SI) fraction of ethyl acetate solvent. [0035] Detailed Description of the Invention [0036] Introduction
[0037] Technology, methods, and processes for efficiently extracting lignin from lignocellulose raw material are revealed by Jansen et. al. in PCT / 2013/039585 and PCT / US2013 / 068824. An overview of lignocellulose biomass processing and refining according to the modalities disclosed here is provided in Figure 1. In general, lignocellulose biomass refining processing and processes include: (1) 1770 pretreatment; (2) 1700 extraction and 1710 hemicellulose sugar purification; and (5) direct extraction of 1760 lignin.
[0038] The processing and refining of lignocellulose biomass begins with pretreatment 1770, during which the lignocellulose biomass can be, for example, dehulled, chipped, shredded, dried, or ground into particles.
[0039] During 1700 hemicellulose sugar extraction, hemicellulose sugars are extracted from the lignocellulose biomass, forming an acidic 1700A hemicellulose sugar vapor and a remaining 1700B lignocellulose stream. The remaining 1700B lignocellulose stream mainly consists of cellulose and lignin.
[0040] In some methods, the remaining 1700-B lignocellulose can be processed to extract lignin. This process produces a high purity 1760-P1 lignin and a high purity 1760-P2 cellulose. The novel lignin purification process of the invention uses a solvent of limited solubility, and can produce a lignin that has a purity greater than 99%. [0041] I. Pre-treatment
[0042] Before extracting 1700 hemicellulose sugar, lignocellulose biomass can be optionally pretreated. The pretreatment refers to the reduction in the size of the biomass (e.g., mechanical decomposition or evaporation), which does not substantially affect the biomass lignin, cellulose and hemicellulose compositions. The pretreatment facilitates the most efficient and economical processing of a downstream process (e.g., extraction of hemicellulose sugar). Preferably, the lignocellulose biomass is peeled, chipped, shredded and / or dried to obtain pretreated lignocellulose biomass. The pretreatment can also use, for example, ultrasonic energy or hydrothermal treatments including water, heat, steam or pressurized steam. Pretreatment can take place or be implemented in several types of containers, reactors, tubes, cells that flow through and the like. In some methods, it is preferred to have pre-treated lignocellulose biomass prior to 1700 hemicellulose sugar extraction. In some methods, no pretreatment is required, ie, lignocellulose biomass can be used directly in 1700 hemicellulose sugar extraction .
[0043] Optionally, the lignocellulose biomass can be crushed or ground to reduce the particle size. In some embodiments, the lignocellulose biomass is milled so that the average particle size is in the range of 100 to 10,000 microns, preferably 400 to 5,000, eg, 100 to 400, 400 to 1,000, 1,000 to 3,000, from 3,000 to 5,000, or from 5,000 to 10,000 microns. In some embodiments, the lignocellulose biomass is milled so that the average particle size is less than 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 1,000, or 400. [0044] II. Extraction of hemicellulose sugar
[0045] The present invention provides an advantageous method of extracting hemicellulose sugars from lignocellulose biomass (1700 hemicellulose sugar extraction). Preferably, an aqueous acid solution is used to extract biomass from lignocellulose. The aqueous acidic solution can contain any acids, inorganic or organic. Preferably, an inorganic acid is used. For example, the solution can be an aqueous acidic solution that contains an inorganic or organic acid such as H2SO4, H2SO3 (which can be introduced as dissolved acid or as SO2 gas), HCl, and acetic acid. The aqueous acidic solution may contain an acid in an amount of 0 to 2% or more, eg, 0 to 0.2%, 0.2 to 0.4%, 0.4 to 0.6% , from 0.6 to 0.8%, from 0.8 to 1.0%, from 1.0 to 1.2%, from 1.2 to 1.4%, from 1.4 to 1.6% , from 1.6 to 1.8%, from 1.8 to 2.0% or more weight / weight. Preferably, the aqueous solution for extraction includes 0.2 to 0.7% H2SO4 and 0 to 3,000 ppm SO2. The pH of the aqueous acidic solution can, for example, be in the range of 1 to 5, preferably 1 to 3.5.
[0046] In some embodiments, a high temperature or pressure is preferred in the extraction. For example, a temperature in the range of 100 to 200 ° C, or more than 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C, or 200 ° C can be used. Preferably, the temperature is in the range of 110 to 160 ° C, or 120 to 150 ° C. The pressure can be in the range of 1 d 10 mPa, preferably 1 to 5 mPa. The solution can be heated for 0.5 to 5 hours, preferably from 0.5 to 3 hours, from 0.5 to 1 hour, from 1 to 2 hours, or from 2 to 3 hours, optionally with a cooling period of one hour.
[0047] Impurities such as ash, acid soluble lignin, fatty acids, organic acids, such as acetic acid and formic acid, methanol, proteins and / or amino acids, glycerol, sterols, rosin acid and fatty materials can be extracted together with hemicellulose sugars under the same conditions. These impurities can be separated from the aqueous phase by solvent extraction (e.g., using a solvent containing amine and alcohol).
[0048] After 1700 hemicellulose sugar extraction, the remaining 1700-B lignocellulose stream can be separated from the 1700-A acidic hemicellulose sugar vapor by any relevant means, including, filtration, centrifugation or sedimentation to form a liquid flow and a solid flow. The 1700-A acidic hemicellulose sugar vapor contains hemicellulose sugars and impurities. The remaining 1700-B lignocellulose stream contains predominantly cellulose and lignin.
[0049] The remaining 1700-B lignocellulose stream can be further flushed to recover additional hemicellulose sugars and acid catalyst trapped within the biomass pores. The recovered solution can be recycled back to the 1700-A acidic hemicellulose sugar vapor, or recycled back to the 1700 hemicellulose sugar extraction reactor. The remaining steam from the remaining 1700-B lignocellulose can be mechanically compressed to increase solid contents (eg, dry solid contents 40 to 60%). The filtrate from the compression step can be recycled back to the 1700-A acidic hemicellulose sugar vapor, or recycled back to the 1700 hemicellulose sugar extraction reactor. Optionally, the remaining 1700-B lignocellulose remnant is ground to reduce particle sizes. Optionally, the remaining compressed lignocellulose is then dried to reduce the moisture content, e.g., less than 15%. The dry matter can be further processed to extract lignin and sugars from cellulose (processes 1720 and 1760 in Figure 1). Alternatively, the dry matter can be pelletized in 1700-P granules, which can be burned as an energy source for the production of heat and electricity or can be used as a raw material for conversion to bio-oil.
[0050] The remaining 1700-B lignocellulose stream can be further processed to extract lignin (process 1760 in Figure 1). Prior to lignin extraction, the remaining 1700-B lignocellulose stream can be separated, washed, and compressed as described above. [0051] III. Extraction of lignin from lignocellulose biomass
[0052] As discussed above with respect to the extraction of hemicellulose sugars, the present invention in one respect provides a new method of extracting lignin directly from lignocellulose biomass after the extraction of hemicellulose sugars. The method uses a solvent of limited solubility, and works well with biomass particles of different sizes. Therefore, it is not necessary to grind the particles before extracting lignin.
[0053] The extraction of hemicellulose sugars from biomass results in a remainder containing lignin. In some methods, extracting sugars from hemicellulose does not remove a substantial amount of cellulose sugars. For example, the extraction of hemicellulose sugars does not remove more than 1, 2, 5, 10, 15, 20, 30, 40, 50, 60% cellulose weight / weight. In some methods, the lignin-containing remnant contains lignin and cellulose. In some methods, the lignin-containing remnant contains less than 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% hemicellulose. In some embodiments, lignin can be directly extracted from lignocellulose biomass without removing sugars from hemicellulose.
[0054] The lignin extraction solution contains a solvent of limited solubility, an acid, and water. Examples of limited solubility solvents suitable for the present invention include methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl propyl ketone, mesityl oxide, diacetyl, 2,3-pentanedione, 2,4-pentanedione, 2,5- dimethylfuran, 2-methylfuran, 2-ethylfuran, 1-chloro-2-butanone, methyl tert-butyl ether, diisopropyl ether, anisol, ethyl acetate, methyl acetate, ethyl formate, isopropyl acetate, propyl acetate, propyl formate, isopropyl formate, 2-phenylethanol, toluene, 1-phenylethanol, phenol, m-cresol, 2-phenylethyl chloride, 2-methyl-2H-furan-3-one, y-butyrolactone, acetal, ethyl acetal methyl, dimethyl acetal, morpholine, pyrrole, 2-picoline, 2,5-dimethylpyridine. In some embodiments, the limited solubility solvent includes one or more esters, ethers and ketones having 4 to 8 carbon atoms. For example, the limited solubility solvent may include ethyl acetate. In some embodiments, the limited solubility solvent essentially consists of, or consists of, ethyl acetate.
[0055] The ratio of the solvent of limited solubility to water suitable for performing the lignin extraction may vary depending on the biomass material and the particular limited solubility solvent used. In general, the solvent to water ratio is in the range of 100: 1 to 1: 100, e.g., from 50: 1 to 1:50, from 20: 1 to 1:20, and preferably 1: 1.
[0056] Several inorganic and organic acids can be used to extract lignin. For example, the solution may contain an inorganic or organic acid, such as H2SO4, HCl, acetic acid and formic acid. The aqueous acidic solution may contain from 0 to 10% of acid or more, eg, from 0 to 0.4%, from 0.4 to 0.6%, from 0.6 to 1.0%, from 1.0 up to 2.0%, from 2.0 to 3.0%, from 3.0 to 4.0%, from 4.0 to 5.0% or more. Preferably, the aqueous solution for extraction and hydrolysis includes from 0.6 to 5%, preferably from 1.2 to 1.5% of acetic acid. The pH of the aqueous acidic solution can, for example, be in the range of 0 to 6.5.
[0057] High temperatures and / or pressures are preferred when extracting lignin. For example, the lignin extraction temperature can be in the range of 50 to 300 ° C, preferably from 160 to 200 ° C, e.g., from 175 to 185 ° C. The pressure can be in the range of 1 to 10 mPa, preferably from 1 to 5 mPa. The solution can be heated for 0.5 to 24 hours, preferably 1 to 3 hours.
[0058] In some embodiments, the pH of the solvent is adjusted to 3.0 to 4.5 (e.g., 3.5 to 3.8). In this pH range, lignin is protonated and is easily extracted in the organic phase. The organic phase comprising solvent and lignin comes in contact with the strong acid cation exchanger to remove residual metal cations. To obtain high-purity solid lignin, the limited solubility solvent is separated from the lignin, e.g., evaporated. Preferably, the limited solubility solvent can be separated from the lignin by mixing the solution of the solvent containing acid lignin with water at an elevated temperature (e.g., 80 ° C). The precipitated lignin can be recovered by, e.g., filtration or centrifugation. The solid lignin can be dissolved in any suitable solvents (e.g., phenylethyl alcohol) to make lignin solutions.
Alternatively, the limited solubility solvent solution containing acid lignin can be mixed with another solvent (e.g., toluene). The solvent of limited solubility can be evaporated while the substitute solvent (e.g., toluene) remains in a solution. A solution of lignin in a desired solvent can be prepared.
[0060] The invention further provides a lignin composition produced by a process of producing high purity lignin from biomass. The process comprises (i) removing hemicellulose sugars from the biomass thereby obtaining a lignin-containing remnant; wherein the remainder containing lignin comprises lignin and cellulose; (ii) contacting the lignin-containing remnant with a lignin extraction solution to produce a lignin extract and a cellulose remnant; wherein the lignin extraction solution comprises a limited solubility solvent, an organic acid, and water, where the limited solubility solvent and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulose remnant; wherein the lignin extract comprises lignin dissolved in the solvent of limited solubility. In some embodiments, the lignin composition is produced by a process that further comprises one, two, three, four, or five additional step (s): (iv) contacting the lignin extract with a strong acid cation exchanger to remove residual cations thereby obtaining a purified lignin extract (v) quickly distill or evaporate the lignin extract thereby removing most of the limited solubility solvent from the lignin extract to obtain solid lignin; (vi) heating the solid lignin in this way to remove solvent with a trace of limited solubility or water from the solid lignin; (vii) employing a vacuum to a solid lignin thereby removing solvent with a trace of limited solubility or water from the solid lignin; and (viii) dissolving the solid lignin with an organic solvent to form a resulting solution and separating the resulting solution from the insoluble remnant.
[0061] In some embodiments, the lignin composition is characterized by at least one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen or nineteen characteristics selected from the group consisting of: (i) aliphatic hydroxyl lignin group in an amount of up to 2 mmole / g; (ii) at least 2.5 mmol / g of phenolic hydroxyl lignin group; (iii) less than 0.40 mmol / g of OH carboxylic lignin group; (iv) sulfur in an amount of up to 1% by weight / weight; (v) nitrogen in an amount of up to 0.5% by weight / weight; (vi) 5% degradation temperature greater than 220 ° C; (vii) 10% degradation temperature above 260 ° C; (viii) less than 1% ash by weight / weight; (ix) a CaHbOc formula; where a is 9, b is less than 12 and c is less than 3.5; (x) a degree of condensation less than 0.9; (xi) a methoxy content of at least 0.8; (xii) an O / C weight ratio of less than 0.4; (xiii) a glass transition elevation between the first and the second heating cycle according to DIN 53765 in the range of 10 to 30 ° C; (xiv) less than 1% carbohydrate by weight / weight; (xv) DMSO solubility is> 100 g / L; (xvi) THF solubility is> 35 g / L; (xvii) solubility in 0.1 N of aqueous NaOH solution is> 8 g / L; (xviii) less than 1% water by weight; and (xix) less than 1% volatile components at 200 ° C by weight.
[0062] In some embodiments, the lignin composition is further characterized as having a glass transition as determined by differential scanning calorimetry (DSC) according to DIN 53765 in the range of 80 ° C to 160 ° C; the DSC thermogram of the second heating cycle is substantially different from the first heating cycle, where the first heating cycle comprises a greater number of exothermic maximums, endothermic maximums or inflection points than the second cycle. In some embodiments, this higher number of points in the first cycle can be attributed to the reactivity of the lignin sample that occurs when heated, due to the heterogeneity of the lignin sample (e.g., a variety of functional groups, molecule structure and molecular weight). In some embodiments, reactivity results in additional crosslinking, resulting in the elevation of the glass transition of the second cycle by more than 5 ° C, 10 ° C, 15 ° C, 20 ° C or even 25 ° C.
[0063] Said thermal behavior is indicative of the instability of the lignin polymer under heat, and possibility under other conditions. For the purposes of industrial application of lignin, it is desirable to have not only the high purity demonstrated for lignin in this invention, but also to have a better defined lignin. This is achieved optionally by fractionating lignin into stable fractions in terms of its thermal behavior, size, structure and other attributes. The stable fractions of lignin will allow the development of lignin as a raw material for chemical conversion processes that break the molecule to obtain valuable chemicals and / or use of lignin as a polymer by combining it with additional components. [0064] IV. Lignin fractionation
[0065] Surprisingly, it has been discovered that said lignin can be fractionated by a robust method to produce two distinct fractions of lignin that are thermally stable and are distinctly different. Then, the invention further provides a lignin composition produced by a process of producing high purity lignin from biomass. The process comprises (i) removing hemicellulose sugars from biomass thereby obtaining a lignin-containing remnant; wherein the remainder containing lignin comprises lignin and cellulose; (ii) placing the lignin-containing remnant in contact with a lignin extraction solution to produce a lignin extract and a cellulose remnant; wherein the lignin extraction solution comprises a limited solubility solvent, an organic acid, and water, where the limited solubility solvent and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulose remnant; wherein the lignin extract comprises lignin dissolved in the solvent of limited solubility. In some embodiments, the lignin composition is produced by a process that further comprises one, two, three, four, or five additional step (s): (iv) bringing the lignin extract into contact with a strong heat exchanger. acid cation to remove residual cations thereby obtaining a purified lignin extract; (v) quickly distill or evaporate the lignin extract, thereby removing most of the limited solubility solvent from the lignin extract to obtain solid lignin; (vi) heat the solid lignin in this way by removing solvent with a trace of limited solubility or water from the solid lignin; (vii) employ a vacuum to the solid lignin thereby removing solvent with a trace of limited solubility or water from the solid lignin; and (viii) bringing the solid lignin into contact with an organic solvent to form a resulting solution comprising the fraction of the lignin, designated as soluble solvent (SS) and a remaining solid designated as insoluble solvent (SI); and separating the resulting solution from the insoluble remainder.
[0066] Solvent fractionation can separate a lignin sample into a soluble fraction (SS) of solvent and fraction of insoluble solvent (si). In some embodiments, this contact is made in a ratio of 1: 3 to 1:10 ratio of solid to liquid (weight / weight), in a container stirred at 20 to 50 ° C for 1 to 10 hours.
[0067] In some embodiments, the solvent is at least a polar organic solvent with a molecular weight less than 200 Da. In some embodiments, the solvent is at least an organic solvent comprising from 1 to 5 carbon atoms, from 0 up to 3 oxygen atoms, and 0 to 6 halogen atoms. In some embodiments, the solvent is a mixture of organic solvents. In some embodiments, the solvent is selected as an organic molecule in which lignin has limited solubility in the solvent. For example, in some embodiments, the solvent is selected so that a 5: 1 weight / weight mixture of the solvent for lignin results in the solubilization of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50% lignin is dissolved in the solvent. In some embodiments, between 10 and 40% of lignin is dissolved in the solvent. In some embodiments, the solubility of lignin in the solvent is at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 85, 80, 95, 97, 98, 99 grams of sample / 500 grams of solvent under the conditions described. In some embodiments, the solvent is an organic molecule in which a sample consisting essentially of lignin has a solubility in the solvent of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20 , 25, 30, 35, 40, 45, 50, 60, 70, 80, 85, 80, 95, 97, 98, 99 gram of sample / 500 grams of solvent under the conditions described. In some embodiments, a mixture of solvents is applied. In some embodiments, at least 30%, 40%, 50%, 60% weight / weight of the lignin solid is soluble in said solvent under the conditions described, but not more than 70%, 60%, 50%, 40% it is soluble. In some embodiments, the solvent is selected to form a fraction of soluble lignin that is at least 2, 4, 6, 8, 10, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 50 , 52% by weight / weight of the total lignin in the sample under the solvent fractionation conditions described here.
[0068] In some embodiments, the solvent is selected from a group consisting of methanol, ethanol, isopropanol, ethyl acetate, ethyl formate and dichloromethane. In some embodiments, the solvent is selected from a group consisting of methanol, ethyl acetate and dichloromethane. In some embodiments, the solvent is methanol. In some embodiments, the solvent is dichloromethane. In some embodiments, the solvent is ethyl acetate.
[0069] In some modalities, the undissolved fraction is collected by filtration, washed and dried with air at 100 to 110 ° C or under vacuum at 45 to 55 ° C. The dissolved fraction is dried by evaporating the solvent or a mixture of the solvent on a rotary evaporator or any other method for evaporating a solvent. The remaining lignin is collected and dried with air at 100 to 110 ° C or under vacuum at 45 to 55 ° C. In some embodiments, the insoluble fraction of the solvent is collected by decanting the solvent from the reactor. In some embodiments, the soluble fraction of the solvent is collected by decanting the solvent out of the insoluble fraction of the fraction.
[0070] The method of fractioning the solvent of a lignin sample can be selected so that the amount of lignin in a soluble fraction of the solvent is low in relation to the amount of lignin in the insoluble fraction of the solvent. For example, in some embodiments of the methods described here, the soluble fraction of the solvent comprises less than 65, 60, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% of the total sample lignin ( weight / weight). In some embodiments, the SS fraction comprises between about 25% and 45% of the total lignin. The method of solvent fractionation of a lignin sample can be selected so that the amount of lignin in the insoluble fraction (SI) of the solvent is low in relation to the amount of lignin in the soluble fraction (SS) of the solvent. For example, in some embodiments of the methods described here, the insoluble fraction of the solvent comprises less than 65, 60, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% of the total sample lignin ( weight / weight). In some embodiments, the SI fraction comprises between about 25% and 45% of the total lignin.
[0071] In some embodiments of the lignin compositions described here, lignin is substantially soluble when the first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and a third amount of insoluble lignin, where the ratio of the second amount of the third amount of lignin is greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 3, 4, 5, 6, 7, 8, 9, 10, or 20 to 1 (weight / weight), and the ratio of the amount of organic solvent to the first amount of lignin is 5: 1 (weight / weight). In some embodiments of the lignin compositions described here, lignin is substantially soluble when the first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and the third amount of insoluble lignin, where the ratio of the second amount to the third amount of lignin is greater than 3: 1 (weight / weight), and the ratio of the amount of organic solvent to the first amount of lignin is 5: 1 (weight / weight).
[0072] In some embodiments of the lignin compositions described here, the lignin is substantially soluble when the first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and the third amount of insoluble lignin, which is greater than 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50% of the first amount of lignin is dissolved in the organic solvent, and in which the ratio of the amount of organic solvent for the first amount of lignin is 5: 1 (weight / weight).
[0073] In some embodiments of the lignin compositions described here, lignin is substantially insoluble when the first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin the third amount of insoluble lignin, where the ratio of the third amount to the second amount of lignin is greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 3, 4, 5, 6, 7, 8, 9, 10, or 20 to 1 (weight / weight), and the ratio of the amount of organic solvent to the first amount of lignin is 5: 1 (weight / weight).
[0074] In some embodiments of the lignin compositions described here, lignin is substantially insoluble when the first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and the third amount of insoluble lignin, where the ratio of the third amount to the second amount of lignin is greater than 3: 1 (weight / weight), and the ratio of the amount of organic solvent to the first amount of lignin is 5: 1 (weight / weight).
[0075] In some embodiments of the lignin compositions described here, lignin is substantially insoluble when the first amount of lignin is stirred for 2 hours at room temperature in the presence of an amount of organic solvent to form a second amount of solubilized lignin and the third amount of insoluble lignin, is greater than 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50% of the first amount of lignin is not dissolved in the organic solvent, and in which the ratio of the amount of organic solvent for the first amount of lignin is 5: 1 (weight / weight).
[0076] The fractionation of the solvent can produce two or more fractions of lignin with chemical compositions different from unfractionated lignin. The chemical composition of each fraction of the fractionated lignin of the solvent can be different from the unfractionated lignin and different from each other fraction. For example, fractions of soluble solvent lignin and / or insoluble solvent lignin may each have a higher oxygen to carbon (O / C) ratio than the 0 / C ratio of unfractionated lignin. The fractions of soluble solvent and / or insoluble solvent lignin can each have a lower hydrogen to carbon (H / C) ratio than the H / C ratio of unfractionated lignin. In some embodiments, the fractional lignin 0 / C and H / C ratios are within 20, 18, 15, 12, 10, 5% unfractionated lignin.
[0077] The chemical composition of each fraction of fractionated lignin in the solvent may be different from unfractionated lignin. For example, the number of OH groups (mmol / g lignin) may be higher in fractionated lignin than in unfractionated lignin. In some modalities, the number of aliphatic, phenolic, and carboxylic OH groups (mmol / g lignin) may be higher in fractionated lignin than in unfractionated lignin. In some embodiments, the SS fraction comprises OH groups that are more phenolic and OH groups that are more carboxylic than the SI fraction (weight / weight).
[0078] The soluble (SS) fractions of solvent and insoluble (si) of solvent obtained by this process share the high purity of lignin solid from which they were made. The two samples are distinctly different in molecular weight, as demonstrated by their characterization side by side by the same gel permeation method.
[0079] In some embodiments, the fraction of soluble lignin (SS) of solvent obtained by the process described here has a low glass transition temperature (Tg) as determined using differential scanning calorimetry (DSC) according to DIN 53765- 1994 For example, the SS fraction may have a Tg measured below the Tg of unfractionated lignin. The SS fraction can have a Tg less than 95, 90, 85, 80, 75, 70, 65, 60, 55, 50 or 45 ° C. The Tg of unfractionated lignin can be in the range of 80 to 160 ° C. The SS fraction can have a Tg less than, 90, 85, 80, 75, 70, 65, or 60 ° C. In some embodiments, the SS fraction has a Tg between about 75 and about 110 ° C. In some embodiments, the SS fraction has a Tg between about 75 and about 95 ° C. For example, the SS fraction may have a Tg measured below the Tg of the solvent insoluble lignin (SI) fraction. The SS fraction can have a Tg less than 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, or 45% of the Tg of solvent insoluble lignin (SI) fraction. In some embodiments, the Tg of the SS Fraction of lignin is stable. In some embodiments, the Tg of the SS lignin fraction varies between the first cycle and the second cycle for less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ° C. In some embodiments, the Tg of the second cycle increases by less than 5 ° C compared to the first cycle in which the first and second DIN cycles are measured within 7, 6, 5, 4, 3, 2, 1, 0 , 5, or 0.1 days each. In some embodiments, the SS fraction does not have Tg at a temperature above room temperature. In some embodiments, the SS fraction is not a polymer.
[0080] In some embodiments, the average number (Mn) molar mass of the SS fraction of lignin is less than the Mn of unfractionated lignin. In some embodiments, the Mn of the SS lignin fraction is less than 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, or 200 Da. The molar mass values disclosed in this invention are determined from according to Asikkala et. al., Journal of agricultural and food chemistry, 2012, 60 (36), 8968 to 73. In some embodiments, the polydispersity (PD) of the SS fraction of lignin is superior to the polydispersity of unfractionated lignin. In some modalities, the PD of the SS fraction is above 3.0, 3.5, 4.0, 4.5, or 5.0. In some embodiments, the average weight molar mass or the average mass molar mass (Mw) of the fraction of soluble lignin (SS) of solvent is less than the Mw of unfractionated lignin. For example, the Mw of the SS lignin fraction may be less than 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 , or 5% Mw of unfractionated lignin. In some embodiments, the Mw of SS lignin fraction is less than 3000, 2900, 2800, 2700, 2600, 2500, 2400, 2300, 2200, 2100, 2000, 1800, 1600, 1500, 1400, 1300, 1200, 1100 , 1000, 900, 970, or 800 Da. In some embodiments, the Mw of the SS fraction is less than 2000 Da. In some embodiments, the fraction of solvent insoluble lignin (SI) obtained by the process described here has a low temperature glass transition (Tg) as determined using differential scanning calorimetry (DSC) according to DIN 53765-1994. For example, the SI fraction can have a Tg measured above the Tg of unfractionated lignin. The SI fraction can have a Tg in more than 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 175, 180, 200, 220, 240, 250 ° C . In some embodiments, the Tg of unfractionated lignin is 80 to 160 ° C. The SI fraction can have a Tg greater than 120, 130, 140, 150, 160, 170, 180, 190, 195, or 200 ° C. In some embodiments, the SI fraction has a Tg between about 14 5 and about 210 ° C. In some embodiments, the SI fraction has a Tg between about 155 and about 200 ° C. For example, the SI fraction may have a Tg measured above the Tg of the solvent soluble lignin (ss) fraction. The SI fraction can have a Tg greater than 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 175, 180, 200, 220, 240, 260, 280, or 300% Tg of solvent soluble lignin (ss) fraction.
[0081] In some modalities, the Tg of the SI lignin fraction is stable. In some embodiments, the Tg of the SI lignin fraction varies between the first cycle and the second cycle for less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ° C. In some embodiments, the Tg of the second cycle increases by less than 5 ° C compared to the first cycle in which the first and second DIN cycles are measured within 7, 6, 5, 4, 3, 2, 1, 0 , 5, or 0.1 days each. In some embodiments, the Tg of the second cycle increases by less than 5 ° C in relation to the first cycle in which the first and second DIN cycles are measured consecutively.
[0082] The size of individual polymeric molecules, and the size distribution of molecules in a sample of polymers, such as lignin can be measured and understood in terms of the average number molar mass (Mn), the average molar mass of mass (Mw), and polydispersity. For lignin samples, the measured values of Mn and Mw (and then polydispersity) may be dependent on experimental conditions. The values revealed here for Mn and Mw of the lignin samples are based on gel permeation chromatography (GPC), using lignin acetobromination, with a LiBr solution in THE as an eluent and UV detection. In some embodiments, the experimental measurement method of Mn and Mw are disclosed in Example 6. In some embodiments, the use of DMSO as an eluant without derivatization can lead to useless measured values of Mn and Mw for a lignin sample. In some modalities, the average number (Mn) molar mass of the SI lignin fraction is greater than the Mn of unfractionated lignin. In some embodiments, the Mn of the SI lignin fraction is more than 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, or 9000 Da. In some embodiments, the polydispersity ( PD) of the SI lignin fraction is less than the polydispersity of unfractionated lignin. In some modalities, the SI fraction PD is less than 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, or 1.4. In some embodiments, the average mass or average weight molar mass (Mw) of the solvent insoluble lignin (SI) fraction is greater than the unfractionated lignin Mw. For example, the SI lignin fraction Mw can be greater than 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1 , 9, 2.0, 2.3, 2.5, 3.0, or 3.5 Mw of unfractionated lignin. In some embodiments, the SI lignin fraction Mw is greater than 5000, 6000, 7000, 8000, 10000, 12000, 14000, 16000, 18000, or 20000 Da. In some embodiments, the SI fraction Mw is greater than 6000 Da.
[0083] Furthermore, the SS fraction and the SI fraction have a distinctly different glass transition temperature, optionally the difference between the transition temperatures of each fraction is greater than 30 ° C, 40 ° C, 50 ° C, 60 ° C. In addition, the glass transition temperature is stable between the first cycle and the second thermal cycle, which has a difference of less than 5 ° C, 4 ° C, 3 ° C, 2 ° C for each fraction. In some embodiments, the SI fraction does not show additional exotherms or endotherms in the DSC scan, indicating that the polymer is stable and does not react in the temperature range up to 250 ° C. [0084] V. Applications of Lignin
[0085] The use of lignin as a precursor to many high-value materials was previously revealed and has been revised in several articles, for example: RJ Gosselink Ph. D Thesis, Wageningen University (2011) "Lignin as a renewable aromatic resource for the chemical industry "; R. J. Gosselink et al, "Valorization of lignin resulting from biorefineries" (2008), RRB4 Rotterdam; D. A. Bulushev and J. R. H. Ross "Catalysis for conversion of biomass to fuels via pyrolysis and gasification: A review" Catalysis Today 171 (2011), pages 1 to 13; A. L. Compere et. al. "Low Cost Carbon Fiber from Renewable Resources" Oak Ridge Labs Report; J. E. Holladay et. al. "Top Value-Added Chemicals from Biomass" Volume II - Results of Screening for Potential Candidates from Biorefinery Lignin, report by Pacific Northwest National Laborator, Oct. 2007.
[0086] The composition of high purity lignin fractionated according to the modalities disclosed here has a more defined character than other lignins. In some embodiments, the SI fraction is a preferred fraction for compound purposes, due to the higher molecular weight, the polymer is not changed by temperature up to 250 ° C as seen in the DSC scan. The SS fraction is a lower molecular weight and soluble solvent is anticipated to be more suitable to be used as a raw material to split lignin into small aromatic molecules of high values. In some embodiments, both the SI fraction and the SS fraction have low oxygen content compared to other lignins, e.g. kraft lignin. In some modalities, the two fractions have a low ash content, a low concentration of sulfur and / or phosphorus. Such a high-purity lignin composition is particularly suitable for use in catalytic reactions by contributing to a reduction in catalyst clogging and / or poisoning. A lignin composition that has a low sulfur content is especially desired for use as fuel additives, for example in gasoline or diesel fuel.
[0087] Some other potential applications for high-purity lignin include carbon fiber production, asphalt production, and as a component in biopolymers. These uses include, for example, oil well drilling additives, concrete additives, dye dispersants, agricultural chemicals, animal feed, industrial binders, specialty polymers for the paper industry, aid for precious metal recovery, wood preservation, sulfur-free lignin products, automotive brakes, wood panel products, biodispersants, polyurethane foams, epoxy resins, printed circuit boards, emulsifiers, sequestering agents, water treatment formulations, power additives for paintings , adhesives, raw materials for vanillin, xylitol, and as a source for paracoumaril, coniferyl, synaphyl alcohol.
[0088] A composition is also provided which comprises a part of lignin as disclosed herein and another ingredient. For example, the composition can comprise up to 98, 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1% by weight / weight of lignin. In some embodiments, the composition comprises up to 50% by weight / weight by weight. In some embodiments, the composition comprises between 5% and 75% lignin, or between 10 and 60% by weight / weight of lignin. In some embodiments, the composition is a polymer, precursor to one or more chemicals, a chemical, or consumer goods. For example, the composition can be selected from the group consisting of fuel additives in gasoline or diesel fuel, carbon fiber, carbon fiber production materials, asphalt, a biopolymer component, oil well drilling additives. oil, concrete additives, dye dispersants, chemicals for agriculture, animal feed, industrial binders, specialty polymers for the paper industry, aid for the recovery of precious metals, materials for wood preservation, sulfur-free lignin products, brakes automotive, wood panel products, biodispersants, polyurethane foams, epoxy resins, printed circuit boards, emulsifiers, sequestering agents, water treatment formulations, power additives for paintings, adhesives, and a material for the production of vanillin , xylitol, paracoumaril, coniferyl, synaphyl alcohol, benzene, xylenes, or toluene.
[0089] In some embodiments, a method is provided which comprises: (i) providing a lignin composition as described here, and (ii) converting at least a part of lignin in the composition to a conversion product. In some embodiments, the conversion involves treating with hydrogen or with a hydrogen donor. In some embodiments, the conversion product comprises a chemical product comprising at least one item selected from the group consisting of bio-oil, carboxylic and fatty acids, dicarboxylic acids, hydroxyl carboxylic acids, hydroxyl di-carboxylic acids and hydroxyl, methylglyoxal, mono-, di- or poly-alcohols, alkanes, alkenes, aromatics, aldehydes, ketones, esters, phenols, benzene, toluenes, and xylenes. In some embodiments, the conversion product is selected from the group consisting of dispersants, emulsifiers, complexers, flocculants, binders, pelletizing additives, resins, carbon fibers, active carbon, antioxidants, liquid fuel, aromatic chemicals, vanillin, adhesives , binders, absorbents, toxin binders, foams, coatings, films, rubbers and elastomers, sequestering agents, fuels, and expanders. In some embodiments, the conversion product comprises a fuel or a combustible ingredient. [0090] Examples
[0091] It is understood that the examples and modalities described here are for illustrative purposes only and are not intended to limit the scope of the claimed invention. It is also understood that several modifications or changes due to the examples and modalities described here will be suggested to people with skill in the art and should be included within the spirit and scope of that request and the scope of the attached claims. All publications, patents, and patent applications cited here are hereby incorporated by reference in their entirety for all purposes. [0092] Example 1 - Small scale hemicellulose sugar extraction
[0093] Table 1 provides a summary of chemical analysis of the resulting fluid body from the extraction of hemicellulose sugar from various types of biomass. 0% monomeric sugar is expressed as% by weight of the total sugar weight. All other results are expressed as% of weight relative to dry biomass.
[0094] All treatments were carried out in a 0.5 L pressure reactor equipped with a stirrer and heating-cooling system. The reactor was discharged with the biomass and liquid in quantities provided in the table. The reactor was heated to the temperature indicated in the table, the time counting was started once the reactor reached 5 ° C below the designated temperature. After the time had elapsed, the reactor was cooled. Solid and liquid were separated, and the content of the obtained fluid body was analyzed, all data were recalculated in relation to the dry biomass weight. HPLC methods were applied to assess the% total sugars in the fluid body,% monomeric sugars and% acetic acid. The% degradation product is the sum of% furfural (GC or HPLC analysis),% formic acid (HPLC) and% levulinic acid (HPLC). The acid soluble lignin was analyzed according to the NREL method TP-510-42627.
[0095] Table 1: Treatment Conditions and chemical analysis of the resulting fluid body
1% total sugars (% TS) measured by HPLC in the fluid body o, DB - Dry Biomass 3% Monomers of total dissolved sugars measured by HPLC in the fluid body 4% acetic acid measured by HPLC in the fluid body 5% Products Degradation =% Furfural +% formic acid +% levulinic acid. % Furfural as measured by GC or HPLC,% formic acid and% levulinic acid measured by HPLC 60.5% H2SO4 + 0.2% SO2 7 0.7% H2SO4 + 0.03% acetic acid [0096] Example 2 - Large scale chemical analysis of lignocellulose matter after hemicellulose sugar extraction
[0097] Table 2 provides a summary of chemical analysis of several types of biomass after extraction of hemicellulose sugar.
[0098] O Pinho (ref A1202102-5): Chips of fresh Loblloly pine (145.9 Lb of dry wood) were fed into a Fast Cycle Digester (RDC, Andritz, Springfield, Ohio). An aqueous solution of acid (500 Lb) was prepared by adding 0.3% H2SO4 and 0.2% SO2 in water to a separate tank. The solution was heated to 135 ° C and then added to the digester to cover the wood. The solution was circulated through the wood for 40 minutes while maintaining the temperature. After 60 minutes, the resulting fluid body was drained into a fluid body tank and using steam, the wood was blown into a cyclone to collect the wood (128.3 Lb of dry wood) and release the steam. The extracted wood was analyzed for sugar content, carbohydrate composition, ash, elements (by ICP), and DCM extracts. Analyzes of hemi-depleted lignocellulose material showed the extraction of 42.4% Arabinane, 10.5% Galactane, 9.6% Xylan, 14.3% Manano, and 11.8% Glucan, indicating that most hemicellulose is extracted. The analyzes also showed 11.6% of "others", including ASL, extractives and ash. The general fraction of carbohydrates in the remaining solid is no different within the measurement error than that of the initial biomass due to this removal of "others". It is therefore easily observed that the extracted wood chips are darker in color and more brittle than fresh biomass.
[0099] Pine (ref A1204131-14 (Kl)): Fresh Loblloly pine chips (145.9 Lb of dry wood) were inserted into a Fast Cycle Digester (RDC, Andritz, Springfield, Ohio). An aqueous solution of acid (500 Lb) was prepared by adding 0.3% H2SO4 and 0.2% SO2 in water to a separate tank. The solution was heated to 135 ° C and then added to the digester to cover the wood. The solution was circulated through the wood for 180 minutes while maintaining the temperature. After 180 minutes, the resulting fluid body was drained into a fluid body tank and using steam, the wood was blown in a cyclone to collect the wood (121.6 Lb of dry wood) and release the steam. The material was analyzed as described above. Analyzes of hemi-depleted lignocellulose material showed extraction of 83.9% Arabinan, 84.3% Galactan, 50.1% Xylan, 59.8% Mananan and no glucan extraction, indicating effective hemicellulose extraction . The analyzes also showed extraction of 21.8% of "others" including lignin, extractives and ash.
[00100] Eucalyptus (ref A120702K6-9): Chips of fresh globulus eucalyptus (79.1 kg of dry wood) were fed into a Fast Cycle Digester (RDC, Andritz, Springfield, Ohio). An aqueous acid solution was prepared by adding 0.5% H2SO4 and 0.2% SO2 in water in a separate tank. The solution was heated to 145 ° C and then added to the digester to cover the wood. The solution was circulated through wood for 60 minutes while maintaining the temperature, then heating was suspended while the circulation continued for another 60 minutes, allowing the solution to cool. After 120 minutes, the resulting fluid body was drained into a fluid body tank and using wood steam it was blown into a cyclone to collect the wood (58.8 kg of dry wood) and release the steam. The material was analyzed as described above. The analyzes showed that 20.1% of the carbohydrates were extracted from the wood xylose (dry wood base) that contains 70% of these sugars, 91% of the sugars in the fluid body present as monomers. Under these conditions the concentration of acetic acid in the fluid body was 3.6% (dry wood base) showing maximum removal of acetate groups from hemicellulose sugars; 4.2% (dry wood base) of acid soluble lignin. These results indicate efficient extraction of hemicellulose and, in particular, xylose, together with hydrolysis of the acetate groups from substituted xylanes. At the same time, a significant amount of soluble acid lignin, extractives and ash are also extracted in the fluid body.
[00101] Table 2: Chemical Analysis of Lignocellulose Matter after Extraction of Hemicellulose Sugar
'Extraction of hemicellulose sugar: 135 ° C for 60 minutes, 0.3% H2SO4, 0.2% SO2. 2Hemicellulose sugar extraction: 135 ° C for 180 minutes, 0.3% H2S04, 0.2% SO2. 3Hemicellulose sugar extraction: 145 ° C for 60 minutes + cooling for 60 minutes, 0.3% H2S04, 0.2% S02. [00102] Example 3 - Direct Lignin Extraction
[00103] After hemicellulose sugars were extracted from eucalyptus chips, the remainder was mainly cellulose and lignin. The remainder was delignified using an organic aqueous solution containing acetic acid according to the procedure described below.
[00104] Eucalyptus wood chips (20.0g) were mixed with a 50/50 v / v solution of methyl ethyl ketone (MEK) and water containing 1.2% acetic acid w / w of solution in a ratio of 1:10 (100mL of water, 100mL of MEK, and 2.2g of acetic acid). The mixture was treated at 175 ° C for 4 hours in a stirred reactor. Then the system was left to cool to 30 ° C before the reactor was opened. The semi-fluid mass was decanted and the solid is collected for further analysis.
[00105] After the reaction, there was 127g of free liquid, of which 47.2g organic and 79.8g aqueous. The organic phase contained 1.5 grams of acetic acid, 10.4 grams of water, and 5.5 grams of dissolved solids (0.1 grams of sugars and 5.4 grams of others, which is mainly lignin). The aqueous phase contained 1.4 g of acetic acid, 2. 1 g of dissolved solids (1.5 g of sugars and 0.6 g of others).
[00106] After decanting the liquid, the black semi-fluid mass and the white precipitate were at the bottom of the flask. This material was vacuum filtered and washed carefully with 50/50 v / v MEK / water (119.3 g MEK 148.4 g water) at room temperature until the color of the liquid became a very light yellow. Three phases were collected; 19.7g organic, 215g aqueous, and 7g dry white solid. The organic phase contained 0.08 g of acetic acid and 0.37 g of dissolved solids. The aqueous phase contained 0.56 g of acetic acid and 0.6 g of dissolved solids.
[00107] All organic phases have been consolidated. The pH of the solution is adjusted to pH 3.8. The solution was then left to separate into an aqueous phase (which contains salts) and an organic phase (which contains lignin). The organic phase containing lignin was recovered and purified using a strong acid cation column. The organic solution was then added dropwise in an 80 ° C water bath to precipitate the lignin.
[00108] Similarly, lignin from bagasse was extracted by pretreated bagasse reaction of sulfuric acid (DS ~ 60%) in a mixture of acetic acid (0.3% w / w of bagasse od), ketone from methyl ethyl, and water at 200 ° C for 160 min. The bagasse to liquid ratio was 1:10 and the liquid phase was 50% v / v MEK for water. The reaction was carried out in a Parr reactor. After the reaction time, the mixture was filtered and the liquid organic phase separated using a separating funnel. The pH of the organic phase was adjusted to ~ 3.8 with sodium hydroxide. Then, the organic phase was passed through SAC resin and added dropwise in an 80 ° C MEK bath. The precipitated lignin is collected by filtration. The lignin was dried in the oven at 105 ° C. [00109] Example 4 - Lignin fractionation
[00110] Lignin from bagasse and eucalyptus raw material was prepared according to Examples 1 to 3. The dry lignin was mixed with a solvent in a 1: 5 weight / weight ratio and stirred for two hours in room temperature. The mixture was filtered and the solvent phase was evaporated under reduced pressure. The two solids (from filtration and evaporation) were dried in the oven at 105 ° C to obtain the soluble fraction (ss) of the solvent and the insoluble fraction (SI) of the solvent. The solvents tested include methanol, ethanol, isopropanol, ethyl acetate, ethyl formate and dichloromethane. It has been anticipated that other solvents may be useful to achieve similar fractionation.
[00111] The soluble (SS) fractions of the solvent and insoluble (si) of the solvent were weighed after fractionation with each of the three solvents (methanol, dichloromethane, and ethyl acetate), and the results are shown in Table 1.
[00112] Table 1. Percentage of fractionation weight of bagasse lignin in different solvents
[00113] Example 5 - Lignin Characterization Methods
[00114] Lignin samples were characterized by elemental analysis (i.e. C, H, 0, N, and S).
[00115] NMR experiments were performed using Bruker Avance-400 spectrometer. Quantitative 13C NMR spectrum was acquired using DMSO-d6 (500 pL) as a solvent for lignin (80 mg), with a reverse closed decoupling sequence, 90 ° pulse angle, 12-s pulse delay, and 12000 scans. Hydroxyl content analyzes were determined using a quantitative 31P NMR procedure. A precise weight (about 40 mg) of a dry lignin sample was dissolved in 500 µl of an anhydrous pyridine / CDCl3 mixture (1.6: 1, v / v). Then, 200 pL of a solution of endo-N-hydroxy-5-norbornene-2,3-dicarboximide (e-NHI) (50 mmol / L serving as an internal standard) and 50 pL of chromium (III) acetylacetonate solution (11.4 mg / mL serving as a relaxation reagent) were added. The internal standard solutions and relaxation reagent were both prepared using an anhydrous pyridine / CDCla (1.6: 1, v / v) mixture. Finally, 100 pL of the phosphorylating reagent 2-chloro-4,4,5,5-tetramethyl-1,2,3-dioxaphospholane) was added, and the mixture was vigorously stirred, transferred into an NMR tube, and subjected to analysis of immediate 31P NMR. The spectrum was acquired using a reverse closed decoupling pulse sequence, 75 ° pulse angle, 10-s pulse delay, and 200 scans.
[00116] Lignin was also thermally characterized by differential scanning calorimetry (DSC) using the standard method number of DIN 53765.
[00117] Gel permeation chromatography (GPC) analysis was performed as shown. Approximately 5mg of lignin was dissolved in 92: 8 (v / v) mixture of glacial acetic acid and acetyl bromide (2 ml) and stirred for two hours at room temperature. Acetic acid and excess acetyl bromide are evaporated with a rotary evaporator connected with a high vacuum pump and a cold trap. The acetylated lignin was immediately dissolved in THE (1mg / ml), filtered and injected into GPC.
[00118] Example 6 - Characterization of the Lignin Structure
[00119] Three lignin samples: unfractionated, and methanol fractionated (SS and SI) were characterized by the methods of Example 5. The original lignin sample was prepared from bagasse according to Examples 1 to 3, was used for prepare SS and SI fractions of lignin according to Example 4. The results are presented in the following section. [00120] Elementary analysis
[00121] Table 2. The elemental analysis and chemical composition of unfractionated and fractionated methanol bagasse lignin including soluble solvent fraction (SS) and insoluble solvent fraction (si).
[00122]

[00123] Additional characterization of fractionated lignin was collected. The results from the elemental analysis of the fractionated lignin in Table 2 did not show significant differences between unfractionated and fractionated lignin. 0 0 / C is slightly higher in insoluble and soluble fractions than an unfractionated one, while H / C is lower. [00124] Hydroxyl content by NMR 31P
[00125] Table 3. The content of fractionated and unfractionated bagasse lignin hydroxyl of methanol as determined by Quantitative NMR 31P
[00126]

[00127] As seen from NMR 31P data (Table 3), after the lignin fractionation the two fractions are structurally different than the unfractionated lignin. The fractionation of methanol resulted in lignin fractions with more aliphatic, phenolic, and carboxylic OH groups. The soluble fraction SS of the solvent contains similar amounts of aliphatic OH as the insoluble fraction. However, the soluble fraction has more phenolic OH and carboxylic OH than insoluble fraction. This is rational considering that more phenolic OH would be required for dissolution. The increase in guaiacyl OH in 31P data is also supported by the decrease in aliphatic bonds as shown in Table 3. The lignin macromolecule opened when mixed with methanol. [00128] Structure Analysis by NMR 13C
[00129] Table 4. Quantitative comparison between fractionated and unfractionated bagasse lignin based on NMR Spectrum 13C

[00130] The NMR 13C spectra of fractional lignin vs. the material before fractionation are consistent with the observation made by NMR 31P that methanol treatment opens some internal bonds in the lignin molecule, as seen in the decrease in methoxy content, (3-0-4 'content, C content -0 aromatic, but not in the aromatic CC content. [00131] Determination of Molecular Weight by GPC
[00132] The gel permeation chromatography (GPC) analysis is performed according to Asikkala et. al., Journal of agricultural and food chemistry, 2012, 60 (36), 8968 to 73. Approximately 5mg of lignin was dissolved in 92: 8 (v / v) mixture of glacial acetic acid and acetyl bromide (2 ml) and stirred for two hours at room temperature. Acetic acid and excess acetyl bromide are evaporated with a rotary evaporator connected with a high vacuum pump and a cold trap. The acetylated lignin was immediately dissolved in THF (1mg / ml), filtered and injected into GPC.
[00133] The molecular weight of the lignin fractions as well as the unfractionated sample was analyzed by GPC. Figure 3 shows fractionation by methanol. NF denotes unfractionated lignin, a soluble SS fraction of the solvent and an insoluble SI fraction of the solvent; Figure 4 shows fractionation by dichloromethane; Figure 5 shows fractionation by ethyl acetate. It is observed that in all cases the soluble fraction of the solvent has a lower MW compared to the insoluble fraction. The results are summarized in Table 5.
[00134] Table 5. GPC analysis of unfractionated and fractionated bagasse lignin
[00135] Thermal Analysis by DSC
[00136] DSC was performed according to DIN 53765: the sample is dried first by a preheating cycle. Then, two consecutive heat cycles were measured, typically in the first cycle, annealing processes occurred that affected the polymer structure, while in the second cycle the higher transition Tg is attributed to the polymer glass transition. The thermograms of unfractionated lignin, the SS fraction and the SI fractions are shown in Figures 6 to 8 and the results are summarized in Table 6.
[00137] Table 6. Thermal Characterization of fractionated and unfractionated methanol bagasse lignin using DSC

[00138] * No Tg points were observed. This could mean that the soluble fraction of DCM is not a polymer.
[00139] The thermogram of the unfractionated lignin, Figure 6A, indicated multiple changes in the lignin polymer at temperatures above 150 ° C and a greater change of 23 ° C in the glass transition between the first and the second cycle. In contrast to this, the thermogram of the soluble methanol fraction (Figure 6B) showed a glass transition at lower temperatures, ca. 117 ° C, consistent with it being the lower molecular weight fraction. The change from cicie 1 to cycle 2 was only 3 ° C and while the thermogram still showed some annealing processes occurring above the glass transition, the extent of these changes is less than in unfractionated lignin. The insoluble fraction of methanol showed a glass transition at a higher temperature, ca. 157 ° C, consistent with this fraction that has higher molecular weight. The thermograms are essentially the same for the first and second cycles (reduction of 2 ° C between cycles), and no endotherms or exotherms observed at temperatures above the glass transition. These thermograms indicate that distinctly two different lignin fractions have been prepared by methanol fractionation treatment. Thermograms also indicate that each fraction is stable under heating, and does not exhibit thermal annealing processes that were observed in the untreated sample as is commonly found in the literature.
[00140] The differential scanning calorimeter (DSC) thermograms of the soluble bagasse lignin (SS) fraction of dichloromethanol solvent and DSC thermogram of the insoluble bagasse lignin fraction (SI) of dichloromethane solvent are shown in Figure 7A and Figure 7B respectively. Dichloromethane fractionated lignin (DCM) provided a soluble fraction of dichloromethane that did not have a Tg point. Without being bound by a particular theory, this could support the claim that the DCM fraction of soluble lignin is not a polymer. However, the insoluble fraction of DCM had a Tg of 167 ° C in the first cycle and 166 ° C in the second cycle. This lignin has a Tg temperature higher than that of unfractionated lignin, and a change in temperature between cycles of only 1 ° C.
[00141] The differential scanning calorimeter (DSC) thermograms of the ethyl acetate solvent soluble bagasse lignin (SS) fraction and the ethyl acetate solvent lignin fraction (SI) DSC thermogram. are shown in Figure 8A and Figure 8B respectively. Lignin fractionated by ethyl acetate provided a soluble fraction with low Tg points (80 and 87 ° C). The insoluble fraction of ethyl acetate had high and stable Tg points of 196 ° C in the first cycle and 192 ° C in the second cycle. This lignin had a Tg temperature higher than that of unfractionated lignin, and a change in temperature between cycles of only 4 ° C.

权利要求:
Claims (14)
[0001]
A method for fractionating lignin which comprises: (i) removing hemicellulose sugars from a biomass, to obtain a lignin-containing remnant, in which the lignin-containing remnant comprises lignin and cellulose; (ii) placing the lignin-containing remnant in contact with a lignin extraction solution to produce a lignin extract and a cellulose remnant; wherein the lignin extraction solution comprises a solvent of limited solubility, an organic acid, and water, in which the solvent of limited solubility and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulose remnant; wherein the lignin extract comprises lignin dissolved in the solvent of limited solubility; characterized by the fact that it comprises one, two or three additional step (s) selected from: (iv) distill or quickly evaporate the lignin extract, thereby removing most of the solubility solvent limited amount of lignin extract to obtain a solid lignin; (v) heat the solid lignin, thereby removing solvent with a trace of limited solubility or water from the solid lignin; and (vi) employ a vacuum in the solid lignin, thereby removing solvent with a trace of limited solubility or water from the solid lignin; and further comprise: (vii) placing a sample comprising solid lignin in contact with an organic solvent to form a resulting biphasic mixture, in which the mixture comprises: a) a remaining solid designated as an insoluble solvent fraction (si) comprising a first fraction of lignin; and b) a liquid solution comprising the solvent and a second fraction of the lignin, in which the second fraction is referred to as the fraction of soluble lignin (ss) of solvent; and (viii) spatially separating the lignin fraction (si) from the lignin fraction (ss); wherein the first lignin fraction and the second lignin fraction have different glass transition temperatures.
[0002]
Method according to claim 1, characterized in that the solvent comprises at least one organic molecule which has up to 5 carbon atoms and at least one heteroatom; contact occurs at 20 to 50 ° C for 1 to 10 hours; spatial separation comprises filtering or decanting the solvent from insoluble lignin; and the method further comprises: (i) evaporating the solvent from the lignin fraction (ss); and (ii) drying each fraction to obtain a fraction of dry solid lignin (ss) and a fraction of dry solid lignin (si); wherein the two fractions of dry solid lignin have different molecular weights as determined by GPC and different consistent glass transition temperatures.
[0003]
Method according to claim 1 or 2, characterized by the fact that at least one of the lignin fractions has a consistent glass transition temperature (Tg) as determined by two consecutive differential scanning calorimetry (DSC) runs of the same part lignin in a single day according to DIN 53765-1994, where a first Tg is measured during the first DSC run, second Tg measured during the second DSC run, and the difference between the first Tg and the second Tg is less than 5 ° C.
[0004]
Method according to claim 3, Q3_22a.ctsrizdo by the fact that the lignin fraction (ss) has a consistent glass transition temperature different from the lignin fraction (si).
[0005]
Method according to any of claims 1 to 4, characterized in that the solvent is selected from the group consisting of methanol, ethanol, isopropanol, ethyl acetate, ethyl formate, dichloromethane, and any mixture thereof.
[0006]
Method according to any one of claims 1 to 5, characterized in that it further comprises converting at least a part of the lignin produced to a conversion product.
[0007]
Method according to claim 6, characterized in that the conversion comprises treating the lignin with hydrogen or a hydrogen donor.
[0008]
Method according to claim 6, characterized in that the conversion product comprises at least one item selected from the group consisting of bio-oil, carboxylic acids and fatty acids, dicarboxylic acids, hydroxyl-carboxylic acid, di-acid - hydroxyl carboxylic and hydroxyl fatty acids, methylglyoxal, mono, di or polyalcohols, alkanes, alkenes, aromatics, aldehydes, ketones, esters, phenols, benzene, toluenes, and xylenes.
[0009]
Method according to claim 6, characterized in that the conversion product is selected from the group consisting of dispersants, emulsifiers, complexing agents, flocculants, binders, pelletizing additives, resins, carbon fibers, active carbon, antioxidants, liquid fuel, aromatic chemicals, vanillin, adhesives, binders, absorbents, toxin binders, foams, coatings, films, rubbers and elastomers, sequestering agents, fuels, and expanders.
[0010]
Lignin composition comprising lignin, where the lignin composition is obtained by a method as defined in any one of claims 1 to 9, and in which the composition is characterized, based on a dry matter, by means of: (I) - a consistent glass transition temperature (Tg) as determined by two consecutive differential scanning calorimetry (DSC) runs of the same part of lignin according to DIN 53765-1994, in which a first Tg is measured during a first run of DSC , a second Tg is measured during a second DSC run, and the difference between the first Tg and the second Tg is less than 10 ° C; a glass transition temperature (Tg) above 160 ° C as determined using differential scanning calorimetry according to DIN 53765-1994; - a mass average molar mass (Mw) greater than 000 Da as measured by gel permeation chromatography; - a numerical mean (MN) molar mass greater than 200 Da as measured by gel permeation chromatography; and - wherein the composition is substantially insoluble in an organic solvent; or (II) - a consistent glass transition temperature (Tg) as determined by two consecutive differential scanning calorimetry (DSC) runs of the same part of lignin according to DIN 53765-1994, in which a first Tg is measured over a first DSC run, a second Tg is measured during a second DSC run, and the difference between the first Tg and the second Tg is less than 10 ° C; a glass transition temperature (Tg) below 100 ° C as determined using differential scanning calorimetry according to DIN 53765-1994; - a mass average molar mass (Mw) less than 500 Da as measured by gel permeation chromatography; - a numerical mean (MN) molar mass less than 000 Da as measured by gel permeation chromatography; and - wherein the composition is substantially soluble in an organic solvent.
[0011]
Composition according to claim 10, in which the composition is further characterized, based on a dry matter, by eleven or more characteristics selected from the group consisting of: i) a polydispersity less than 7.00 as measured by gel permeation chromatography; ii) a CgHzOy formula; where x is less than 12 and y is less than 3.5; iii) a degree of condensation less than 0.8 as determined by nmr; iv) methoxy content (# / aryl group) as determined by nmr less than 1.4; v) aliphatic bonds (p-O-4 ') (# / aryl group) less than 0.6; vi) ratio of aromatic C-0: aromatic C-C: aromatic C-H (# / aryl group) 1.6: 2.3: 2.1 or 1.6: 2.2: 2.2; vii) an amount of aromatic C-0 bonds (# / aryl group) less than 2.1; viii) elemental composition of greater than 61% carbon, less than 27% oxygen, and less than 0.5% nitrogen by mass as measured by elementary analysis; ix) a marker molecule at a concentration of at least 100 ppb; x) less than 0.1 times the volatile sulfur compounds found in kraft lignin; xi) an ash content of less than 0.5%; xii) a sulfur content less than 700 ppm; xiii) a phosphorus content less than 100 ppm; and xxi) a soluble carbohydrate content of less than 0.5%.
[0012]
Composition according to claim 10 or 11, comprising a marker molecule in a concentration of at least 100 ppb, characterized by the fact that the marker molecule is optionally selected from the group consisting of isopropanol, ethyl acetate, ethyl format , dichloromethane, hexanol, furfural, furfural hydroxymethyl, 2,3,5 trimethyl furan, p-hydroxyphenoxyacetic acid, 4-hydroxy-3,5, -dimethoxyphenyl acetic acid, methyl ethyl ketone, methylpropenyl ketone, 3- ( 2-furyl) -3-penten-2-one, 3-methyl-2-pentene-4-one, 3,4-dimethyl-4-hexene-one, 5-ethyl-5-hexene-3-one, 5 -methyl-4-heptene-3-one, o-hydroxyanisole, 3-ethyl-4-methyl-3-pentene-2-one, 3,4,4-trimethyl-2-cyclohexene-l-one, 2'- hydroxy-4 ', 5'-dimethylacetophenone, methanol, 1- (4-hydroxy-3-methoxyphenyl) propane, galcturonic acid, dehydroabietic acid, glycerol, fatty acids and resin acids.
[0013]
Composition according to any one of claims 10 to 12, characterized in that it comprises ash in an amount less than 0.5%.
[0014]
Composition according to any one of claims 10 to 13, characterized in that the organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, ethyl acetate, ethyl formate, dichloromethane and any mixture thereof.

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Wang et al.2021|Molecular Structure of Poplar Lignin Obtained by p-Toluene Sulfonic Acid | and Formic Acid Delignification.

---

WO2020263170A1|2020-12-30|Processes for obtaining substances from bark and a composition containing bark for use in the processes

---

WO2021074210A1|2021-04-22|Production of fragments of lignin with functional groups

同族专利:

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公开号 | 公开日

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CA2911484A1|2014-11-06|

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EP2991998A1|2016-03-09|

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US20160102113A1|2016-04-14|

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BR112015027743A2|2017-07-25|

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US20180079766A1|2018-03-22|

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US9683005B2|2017-06-20|

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CN105358608B|2018-11-16|

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JP2016516882A|2016-06-09|

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US9988412B2|2018-06-05|

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BR112015027743B8|2021-01-26|

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EP2991998B1|2019-08-14|

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CN105358608A|2016-02-24|

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WO2014179777A1|2014-11-06|

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KR20160007537A|2016-01-20|

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JP2019163466A|2019-09-26|

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CA2911484C|2021-05-25|

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EP2991998A4|2016-03-09|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2380448A|1941-01-25|1945-07-31|Northwood Chemical Company|Lignin and method of production|

---

US2772965A|1953-06-02|1956-12-04|Rayonier Inc|Recovery of chemicals in wood pulp preparation|

---

US3808192A|1973-04-11|1974-04-30|Westvaco Corp|Production of high surface area lignins by spray drying|

---

NL188659C|1975-02-21|1992-08-17|Shell Int Research|PROCESS FOR DESULFULIFYING HYDROCARBON OILS|

---

US4111928A|1975-08-28|1978-09-05|Holsopple Dale B|Method of separating lignin and making epoxide-lignin|

---

DE2737118C2|1977-08-17|1989-06-15|Bau- Und Forschungsgesellschaft Thermoform Ag, Murten, Fribourg, Ch|

---

US4470851A|1981-03-26|1984-09-11|Laszlo Paszner|High efficiency organosolv saccharification process|

---

US4237110A|1979-04-30|1980-12-02|The Dow Chemical Company|Process for separating and recovering concentrated hydrochloric acid from the crude product obtained from the acid hydrolysis of cellulose|

---

US4277626A|1980-01-24|1981-07-07|Forss Kaj G|Method for the isolation of vanillin from lignin in alkaline solutions|

---

JPS59204997A|1983-04-28|1984-11-20|Takara Shuzo Co|Total utilizable treatment of plant biomas resources|

---

CA1258736A|1985-10-29|1989-08-22|National Research Council Of Canada|Preparation of substituted polysulfones bymetalation|

---

CA1267648A|1985-11-05|1990-04-10|Raphael Katzen|Process for lignin recovery|

---

US4740591A|1987-04-13|1988-04-26|Westvaco Corporation|Lignin by-products of paper-making process|

---

CA1278294C|1987-09-17|1990-12-27|George S. Ritchie|Method for fractionation of lignins from steam exploded lignocellulosics to provide fractions with different, but reproducible properties,and some methods for their interconversions and the products so produced|

---

JPH0329887B2|1988-06-06|1991-04-25|

---

EP0364632A1|1988-10-17|1990-04-25|Zeneca Limited|Production of lignin|

---

EP0763622A3|1990-08-17|1999-08-25|Alcell Technologies Inc.|Continuous solvent pulping and washing processes and apparatus|

---

US5730837A|1994-12-02|1998-03-24|Midwest Research Institute|Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars|

---

CA2221619A1|1995-06-07|1996-12-19|Gopal C. Goyal|Modified organosolv pulping|

---

US6022419A|1996-09-30|2000-02-08|Midwest Research Institute|Hydrolysis and fractionation of lignocellulosic biomass|

---

US5968417A|1997-03-03|1999-10-19|The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration|Conducting compositions of matter|

---

AU1584201A|1999-11-02|2001-05-14|Waste Energy Integrated Sytems, Llc|Process for the production of organic products from lignocellulose containing biomass sources|

---

CN1242936C|2000-03-16|2006-02-22|Tfm汉德尔斯股份公司|Sulphur-free lignin and derivatives thereof for reducing the formation of slime and deposits in industrial plants|

---

NO312070B1|2000-07-04|2002-03-11|Karl Weydahl|Process of a process for the production of processable sugar from cellulosic raw materials|

---

US6419788B1|2000-08-16|2002-07-16|Purevision Technology, Inc.|Method of treating lignocellulosic biomass to produce cellulose|

---

DE10100595A1|2001-01-09|2002-07-18|Joerg Peter Schuer|Process for non-toxic odor neutralization of air|

---

DE10109502A1|2001-02-28|2002-09-12|Rhodia Acetow Gmbh|Removal of hemicellulose from biomaterial, especially wood pulp, involves extraction by treatment with an aqueous solution of metal complex, e.g. nickel tris-2-aminoethyl-amine di-hydroxide|

---

US20030221804A1|2002-06-03|2003-12-04|Lightner Gene E.|Lignins derived from black liquor|

---

AU2003281334A1|2002-07-02|2004-01-23|Andritz, Inc.|Solvent pulping of biomass|

---

WO2004106624A1|2003-06-03|2004-12-09|Pacific Pulp Resources Inc.|Method for producing pulp and lignin|

---

CN1886700A|2003-12-05|2006-12-27|佳能株式会社|Toner and process for producing toner|

---

US7250241B2|2003-12-05|2007-07-31|Canon Kabushiki Kaisha|Toner and process for producing toner|

---

BRPI0500534A|2005-02-15|2006-10-10|Oxiteno Sa Ind E Comercio|acid hydrolysis process of cellulosic and lignocellulosic materials, digestion vessel and hydrolysis reactor|

---

US20090017503A1|2005-08-05|2009-01-15|The Trustees Of Dartmouth College|Method and Apparatus for Saccharide Precipitation From Pretreated Lignocellulosic Materials|

---

BRPI0505212A|2005-11-01|2007-08-07|Dedini Sa Ind De Base|improvements in fast acid hydrolysis process of lignocellulosic material and hydrolysis reactor|

---

WO2007120210A2|2005-11-23|2007-10-25|Natureworks Llc|Process for fractionating lignocellulosic biomass into liquid and solid products|

---

BRPI0711751A2|2006-05-08|2012-01-03|Biojoule Ltd|Process for the production of biofuel from plant materials|

---

US20090062516A1|2006-05-08|2009-03-05|Biojoule Limited|Lignin and other products isolated from plant material, methods for isolation and use, and compositions containing lignin and other plant-derived products|

---

WO2008017145A1|2006-08-07|2008-02-14|Emicellex Energy Corporation|Process for recovery of holocellulose and near-native lignin from biomass|

---

US7666637B2|2006-09-05|2010-02-23|Xuan Nghinh Nguyen|Integrated process for separation of lignocellulosic components to fermentable sugars for production of ethanol and chemicals|

---

US7699958B2|2006-11-27|2010-04-20|Ut-Battelle, Llc|Method for improving separation of carbohydrates from wood pulping and wood or biomass hydrolysis liquors|

---

US20100279361A1|2007-05-02|2010-11-04|Mascoma Corporation|Two-stage method for pretreatment of lignocellulosic biomass|

---

US8193324B2|2007-05-31|2012-06-05|Lignol Innovations Ltd.|Continuous counter-current organosolv processing of lignocellulosic feedstocks|

---

US20080295980A1|2007-05-31|2008-12-04|Lignol Innovations Ltd.|Continuous counter-current organosolv processing of lignocellulosic feedstocks|

---

CA2687916C|2007-05-31|2016-01-19|Lignol Innovations Ltd.|Concurrent anaerobic digestion and fermentation of lignocellulosic feedstocks|

---

US7794824B2|2007-06-25|2010-09-14|Weyerhaeuser Nr Company|Carbon fibers from kraft softwood lignin|

---

US7678358B2|2007-06-25|2010-03-16|Weyerhaeuser Nr Company|Carbon fibers from kraft softwood lignin|

---

EP2025735A1|2007-08-14|2009-02-18|Bergen Teknologioverforing AS|One-step conversion of solid lignin to liquid products|

---

BRPI0815822A2|2007-08-31|2017-05-16|Biojoule Ltd|lignin and other products from plant material, and methods and compositions for these.|

---

CN101143881B|2007-10-11|2011-03-16|孔延华|Method for synchronously extracting hemicellulose, cellulose and lignin and reclaiming phenolic acid compounds|

---

ES2326455B2|2007-11-27|2010-02-26|Universidad De Sevilla|PROCEDURE FOR THE MANUFACTURING IN AMBIENT TEMPERATURE OF MICRO AND NANOFIBERS OF LIGNINA AND OTHER RESINOSUS COMPOUNDS.|

---

EP2247785B1|2008-02-21|2019-12-18|Valmet AB|A method for separating lignin from black liquor, a lignin product, and use of a lignin product for the production of fuels or materials|

---

PT2254913T|2008-03-14|2017-10-23|Virginia Tech Intellectual Properties Inc|Method for lignocellulose pretreatment using a super-cellulose-solvent and highly volatile solvents|

---

US8895290B2|2008-10-17|2014-11-25|Maxbiogas Gmbh|Method for digesting a biomass comprising lignin together with cellulose and/or hemicellulose|

---

BRPI0919771A2|2008-10-17|2015-08-18|Mascoma Corp|Pure lignin production from cellulosic ligno biomass|

---

US8216809B2|2008-12-19|2012-07-10|E I Du Pont De Nemours And Company|Organic solvent pretreatment of biomass to enhance enzymatic saccharification|

---

TW201031692A|2009-01-15|2010-09-01|Toho Tenax Europe Gmbh|Lignin derivative, shaped body comprising the derivative and carbon fibres produced from the shaped body|

---

BRPI1007047A2|2009-01-16|2015-08-18|Lignol Innovations Ltd|Whole sugarcane biorrefino irganosolv.|

---

SI2421911T1|2009-04-23|2014-10-30|Greenfield Ethanol Inc.|Separation of reactive cellulose from lignocellulosic biomass with high lignin content|

---

KR20100119018A|2009-04-30|2010-11-09|삼성전자주식회사|Pretreatment method of lignocellulose-based biomass|

---

EP2435453B1|2009-05-28|2022-03-02|Suzano Canada Inc.|Derivatives of native lignin|

---

GB0910707D0|2009-06-19|2009-08-05|Weyland As|Method|

---

EP2454409B1|2009-07-13|2013-12-18|BETA RENEWABLES S.p.A.|High temperature lignin separation process|

---

WO2011037967A2|2009-09-25|2011-03-31|Lake Michael A|Process for recovering lignin|

---

US8790542B2|2009-09-30|2014-07-29|Sandia Corporation|Compositions and methods useful for ionic liquid treatment of biomass|

---

GB0921666D0|2009-12-10|2010-01-27|Cambridge Biopolymers Ltd|Resins|

---

WO2011097721A1|2010-02-15|2011-08-18|Lignol Innovations Ltd.|Carbon fibre compositions comprising lignin derivatives|

---

JP2011256380A|2010-05-14|2011-12-22|Mie Univ|Lignin-based material, method for production thereof, and use thereof|

---

US20140242867A1|2011-04-07|2014-08-28|Robert Jansen|Lignin compositions, methods of producing the compositions, methods of using lignin compositions, and products produced thereby|

---

EP2609104A1|2010-06-03|2013-07-03|Virdia Ltd|Lignin compositions, systems and methods for processing lignin and/or hcl|

---

CA2799798C|2010-06-03|2015-01-20|Fpinnovations|Method for separating lignin from black liquor|

---

IL207329D0|2010-08-01|2010-12-30|Robert Jansen|A method for refining a recycle extractant and for processing a lignocellulosic material and for the production of a carbohydrate composition|

---

US20130183227A1|2010-09-23|2013-07-18|Toho Tenax Europe Gmbh|Thermoplastic lignin for producing carbon fibers|

---

US20120226029A1|2010-09-28|2012-09-06|Weyerhaeuser Nr Company|LOW Tg LIGNIN|

---

PT106039A|2010-12-09|2012-10-26|Hcl Cleantech Ltd|PROCESSES AND SYSTEMS FOR PROCESSING LENHOCELLULOSIC MATERIALS AND RELATED COMPOSITIONS|

---

FI126512B|2011-03-09|2017-01-13|Nanorefix Oy|Method for separating lignin from plant material and product obtained|

---

WO2012151524A2|2011-05-04|2012-11-08|Renmatix, Inc.|Lignin production from lignocellulosic biomass|

---

JP2012236811A|2011-05-09|2012-12-06|Kono Shinsozai Kaihatsu Kk|Purified lignin and epoxy resin|

---

WO2012155074A1|2011-05-12|2012-11-15|Virent, Inc.|Process for purifying lignocellulosic feedstocks|

---

JP2013035885A|2011-08-03|2013-02-21|Asahi Organic Chemicals Industry Co Ltd|Lignin, composition containing lignin and method for producing the lignin|

---

JP2013035886A|2011-08-03|2013-02-21|Asahi Organic Chemicals Industry Co Ltd|Lignin, composition containing the lignin and method for producing the lignin|

---

CA2858651C|2011-12-09|2021-01-26|Upm-Kymmene Corporation|A method for making a lignin component, a lignin component and its use and a product|

---

AU2013256049B2|2012-05-03|2017-02-16|Virdia, Inc.|Methods for treating lignocellulosic materials|

---

US9657146B2|2013-03-14|2017-05-23|Virdia, Inc.|Methods for treating lignocellulosic materials|

---

BR112015027744A8|2013-05-03|2019-04-16|Virdia Inc|methods for treating lignocellulosic materials|

---

WO2014046826A1|2012-09-20|2014-03-27|Graftech International Holdings Inc.|Carbon fibers derived from lignin|

---

SE537712C2|2012-11-13|2015-10-06|Stora Enso Oyj|Thermally reactive thermoplastic intermediate comprising conifers lignin and process for the preparation thereof.|

---

US9758905B2|2012-11-16|2017-09-12|Graftech International Holdings Inc.|Process of making carbon fibers derived from lignin/carbon residue|

---

RU2661893C2|2013-01-25|2018-07-23|Рен Фьюэл К2Б Аб|Compositions of biomass materials for refining|

---

US9365525B2|2013-02-11|2016-06-14|American Science And Technology Corporation|System and method for extraction of chemicals from lignocellulosic materials|

---

US10059730B2|2013-03-15|2018-08-28|Renmatix, Inc.|High purity lignin, lignin compositions, and higher structured lignin|

---

EP2991998B1|2013-05-03|2019-08-14|Virdia, Inc.|Methods for preparing thermally stable lignin fractions|

---

JP6687594B2|2014-07-09|2020-04-22|ヴァーディア， インコーポレイテッド|Method for separating and purifying lignin from black liquor and composition thereof|BR112015027744A8|2013-05-03|2019-04-16|Virdia Inc|methods for treating lignocellulosic materials|

---

US9657146B2|2013-03-14|2017-05-23|Virdia, Inc.|Methods for treating lignocellulosic materials|

---

AU2013256049B2|2012-05-03|2017-02-16|Virdia, Inc.|Methods for treating lignocellulosic materials|

---

EP2991998B1|2013-05-03|2019-08-14|Virdia, Inc.|Methods for preparing thermally stable lignin fractions|

---

EP2918640A1|2014-03-13|2015-09-16|Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO|Bitumen composition|

---

JP6687594B2|2014-07-09|2020-04-22|ヴァーディア， インコーポレイテッド|Method for separating and purifying lignin from black liquor and composition thereof|

---

WO2017051911A1|2015-09-25|2017-03-30|出光興産株式会社|Method for producing purified lignin, purified lignin, resin composition and molded body|

---

CA3029301A1|2016-04-13|2017-10-19|Ecole Polytechnique Federale De Lausanne |Production of monomers from lignin during depolymerisation of lignocellulose-containing composition|

---

KR101809564B1|2016-06-14|2017-12-15|에스이켐 주식회사|A method for purifying lignin from the biomass and the plastic materials comprising lignin prepared therefrom|

---

WO2017222084A1|2016-09-09|2017-12-28|出光興産株式会社|Production method for product derived from plant-based biomass having two-stage process|

---

CN106698581B|2017-01-17|2020-05-05|河北工业大学|Adsorption treatment method of cationic dye|

---

CN107502249B|2017-08-31|2020-12-25|南京工业大学|Method for preparing lignin-based phenolic resin adhesive and co-producing fast-rotting returning fertilizer by using cellulosic ethanol fermentation residues|

---

CN107699173B|2017-08-31|2018-11-20|南京工业大学|A method of phenolic resin adhesive is prepared using classification lignin|

---

CA3110458A1|2017-08-31|2019-03-07|Attis Ip, Llc|Method for separating and recovering lignin and meltable flowable biolignin polymers|

---

CN108279255B|2018-02-09|2021-01-26|山东省水利科学研究院|Large-scale hydraulic engineering seepage flow real-time detection device|

---

GB201817972D0|2018-11-02|2018-12-19|Imperial Innovations Ltd|Adsorption of lignin|

---

CN109518209B|2019-01-15|2020-08-25|河北工业大学|Method for preparing 3-tert-butyl 4-hydroxyanisole by electrocatalysis of 4-hydroxyanisole unit and tert-butyl chloride in lignin|

---

EP3922664A1|2020-06-10|2021-12-15|Borealis AG|Stable lignin-phenol blend for use in lignin modified phenol-formaldehyde resins|

法律状态:
2017-10-03| B25G| Requested change of headquarter approved|Owner name: VIRDIA, INC. (US) |

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2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-05-21| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-06-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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2020-10-06| B09W| Decision of grant: rectification|Free format text: REFERENCIA: RPI 2572 DE 22.04.2020 - CODIGO 9.1. |

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2020-11-17| B09W| Decision of grant: rectification|Free format text: RETIFICACAO DA PUBLICACAO 9.1 - RPI 2572 DE 22/04/2020 |

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2020-11-24| B09Y| Publication of grant cancelled|Free format text: REFERENCIA: RPI NO 2596 DE 06/10/2020, CODIGO 9.1.4 |

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2021-01-26| B16C| Correction of notification of the grant|Free format text: REFERENTE A RPI 2581 DE 23/06/2020, QUANTO AO DESENHO. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361819485P| true| 2013-05-03|2013-05-03|

---

US61/819,485|2013-05-03|

---

US201461953572P| true| 2014-03-14|2014-03-14|

---

US61/953,572|2014-03-14|

---

PCT/US2014/036704|WO2014179777A1|2013-05-03|2014-05-02|Methods for preparing thermally stable lignin fractions|

---