CN110540508B - Eutectic solvent and application thereof in extracting lignin - Google Patents
Eutectic solvent and application thereof in extracting lignin Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The disclosure belongs to the technical field of biomass refining, and particularly relates to a eutectic solvent and application thereof in lignin extraction. The eutectic solvent consists of a certain amount of hydrogen bond donors and hydrogen bond acceptors, and is an economic and environment-friendly green solvent. Wherein, the choline eutectic solvent has wide application in the aspect of extracting lignocellulose. The inventors found that the presence of chloride ions in the eutectic solvent of choline chloride concentrates the negative charge distribution, reduces the extraction efficiency, and accelerates the aging of the apparatus. The present disclosure provides a low-halogen eutectic solvent, wherein organic acid radical ions are adopted to replace halogen anions in choline chloride. The disclosed research proves that the method has the advantages of high lignin extraction rate, high purity, simple operation, obvious effect, strong practicability, little pollution and easy popularization.
Description
Technical Field
The disclosure belongs to the technical field of biomass refining, and particularly relates to a low-halogen-content eutectic solvent and application of the solvent system in extraction and separation of lignin.
Background
The information in this background section is only for enhancement of understanding of the general background of the disclosure and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the increasing shortage of petrochemical resources and the increasing pressure of environmental pollution, the search for a renewable resource for replacing petrochemical resources becomes important for sustainable development. The wood biomass resource mainly comprises cellulose, hemicellulose and lignin, and is the most widely available renewable resource with the most abundant content on the earth. Therefore, the development and utilization of the woody biomass resources are important ways to solve resource crisis and energy crisis, and the realization of the high-efficiency separation and high-valued utilization of all components of the lignocellulose is also paid more and more attention by people.
The lignin is one of the main components of the wood biological resources, is a renewable aromatic polymer with the most abundant content on the earth, is the only non-petroleum resource capable of providing renewable aromatic compounds in nature, and has the potential of replacing non-renewable resources such as petroleum. Lignin is mainly present in the cell wall of plants, and is the second largest biomass resource next to cellulose, but due to its complex structure, it causes difficulties in separation. The traditional separation methods mainly comprise an organic solvent extraction method, an enzyme hydrolysis method and an acid treatment method, but the methods have the defects of low dissolution rate, large solvent pollution, difficult solvent recovery and the like, and the high-value utilization of lignin is hindered. Therefore, a green solvent is needed to be searched for the efficient separation of lignin from woody biomass.
Eutectic solvents are mixtures of stoichiometric hydrogen bond donors and hydrogen bond acceptors that have melting points much lower than the melting points of the individual components by van der waals forces and strong hydrogen bonding between the components. The eutectic solvent has the advantages of good chemical stability, nonflammability, non-volatility, low cost, reusability and the like, and is an economic and environment-friendly green solvent. The choline eutectic solvent has good dissolving capacity on lignocellulose, and can dissolve and separate most of lignin from the wood fiber raw material in the pretreatment process. Meanwhile, the extracted lignin has the characteristics of high purity and small molecular weight, can be used for producing various products with high added values, and has great application prospect.
The inventor finds that at present, the deep eutectic solvent of choline chloride is mainly used for extracting lignin, choline chloride is used as a hydrogen bond receptor, various organic acids, urea and the like are used as hydrogen bond donors, and the deep eutectic solvent has strong fiber dissolving capacity and good lignin purification effect. However, due to the presence of chloride ions, the negative charge distribution is too concentrated and requires higher temperatures to reach its melting point and to react well with the fibers (Hedgeon, Securon, Suxiaojun, et al, research advances on Ionic liquids dissolving lignocellulose and its components [ J ]. chemical and biological engineering, 2012,29(9):1-5.), and the pyrolysis products may cause fibrosis (Ebner G, Schiehser S, Potthaust A, et al. site reaction of cellulose with common 1-alkyl-3-methyl-zolimide-based Ionic acids [ J ]. Tetrahedron Letters,2008,49(51): 7322. 7324.), and toxic metal halides (Gorman-Lewis D J, Fein J. Example Study of the Adsorption of the biological acids [ J.: 2495. and 50. scientific J. (2438, technique, 2438, III, et al. research). While causing corrosion of the apparatus and accelerated equipment aging during use (Arenas M F, reduce R G. Corrosion of steel in ionic liquids [ J ]. Journal of Mining & metals, 2003,39(1-2): 81-91.).
Disclosure of Invention
Against the background of the above research, the inventors believe that, for example, the chlorine ions in the choline eutectic solvent can be replaced, and a eutectic solvent with low halogen content is provided, so that the extraction effect of lignin can be effectively improved, and the equipment loss can be reduced. In order to achieve the technical purpose, the inventor adjusts a hydrogen bond acceptor and a hydrogen bond donor in a eutectic solvent system, and replaces halogen anions in choline chloride with organic acid radical ions, so as to disperse the anionic charge density of the eutectic solvent and improve the extraction efficiency of lignin; meanwhile, the halogen content of the eutectic solvent is reduced by removing the chloride ions, and the corrosion problem caused by the halogen ions is avoided.
In order to achieve the technical effects, the present disclosure provides the following technical solutions:
in a first aspect of the present disclosure, a eutectic solvent is provided, the eutectic solvent includes a hydrogen bond acceptor and a hydrogen bond donor, the hydrogen bond acceptor is a choline ionic liquid, and the structural formula is:
wherein: the cation is choline cation; the anion (X-) is chloride ion or one or more of formate, acetate, propionate, butyrate, lactate, glycinate, lysinate, arginate, alaninate, glutamate and hydrogen sulfate;
the hydrogen bond donor is one or more of formic acid, acetic acid, propionic acid, butyric acid, lactic acid, urea, glycerol, levulinic acid, glycine, lysine, arginine, alanine, glutamic acid, oxalic acid, citric acid, p-toluenesulfonic acid and the like.
In a second aspect of the present disclosure, there is provided the use of the eutectic solvent of the first aspect in the extraction of lignin.
In a third aspect of the present disclosure, there is provided a method for extracting lignin, the method comprising extracting with the eutectic solvent of the first aspect.
Compared with the prior art, the beneficial effect of this disclosure is:
(1) the lignin obtained by the process disclosed by the invention has high extraction rate, high purity and low molecular weight, and is beneficial to the production of high-valued lignin products, so that the utilization value of the lignin is improved.
(2) The synthetic eutectic solvent used in the present disclosure has high drug bioaffinity and less environmental pollution.
(3) The eutectic solvent used in the present disclosure has no special requirements for equipment, is low in cost, and can be reused through multiple cycles.
(4) The treatment method disclosed by the invention is simple, strong in practicability, low in cost and easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
FIG. 1 is an FT-IR spectrum of lignin extracted from the eutectic solvent in examples 1-3.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the choline eutectic solvent has better dissolving capacity and lignin purification effect on lignocellulose. However, the presence of chloride ions in this type of eutectic solvent reduces the solvent extraction efficiency and accelerates the aging of the apparatus. In order to solve the above technical problems, the present disclosure proposes a low halogen content eutectic solvent system.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific examples and comparative examples.
The amounts of reagents and chemicals used below are relative to the mass of oven-dried wood flour unless otherwise specified. The concentrations and the solid-to-liquid ratios referred to below are mass percentages unless otherwise specified.
In a first aspect of the present disclosure, a eutectic solvent is provided, the eutectic solvent includes a hydrogen bond acceptor and a hydrogen bond donor, the hydrogen bond acceptor is a choline ionic liquid, and the structural formula is:
wherein: the cation is choline cation; the anion (X-) is chloride ion or one or more of formate, acetate, propionate, butyrate, lactate, glycinate, lysinate, arginate, alaninate, glutamate and hydrogen sulfate;
the hydrogen bond donor is one or more of formic acid, acetic acid, propionic acid, butyric acid, lactic acid, urea, glycerol, levulinic acid, glycine, lysine, arginine, alanine, glutamic acid, oxalic acid, citric acid, p-toluenesulfonic acid and the like.
Preferably, the hydrogen bond acceptor and the hydrogen bond donor are mixed according to the amount of the substance of 1: 1-1: 20.
Preferably, the hydrogen bond acceptor and the hydrogen bond donor are mixed and then heated and stirred for 1-8 hours at the temperature of 30-80 ℃ to obtain the eutectic solvent.
Preferably, the eutectic solvent hydrogen bond acceptor is prepared by modification according to the literature description (Ferguson J L, Holbrey J D, Ng S, et al. A greener, halide-free early to ionic liquid synthesis [ J ]. Pure and Applied Chemistry,2011,84(3): 723-; adding acid into the supernatant, and drying to obtain the hydrogen bond receptor.
More preferably, the choline chloride and the potassium hydroxide are mixed in a mass ratio of 1: 1-1: 2.
Further preferably, the alcohol solvent is ethanol.
Preferably, the choline chloride and the potassium hydroxide are heated and stirred for 1-8 hours at 20-80 ℃ in the alcohol solvent.
In some specific embodiments, the hydrogen bond acceptor and the hydrogen bond donor are mixed according to the mass ratio of 1:10, and the mixture is heated and stirred for 5 hours at the reaction temperature of 60 ℃.
More preferably, the acid is added to the choline chloride and the potassium hydroxide in a ratio of 1:0.5 to 1: 5.
More preferably, the acid is hydrochloric acid or one or more of formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycine, lysine, arginine, alanine, glutamic acid, sulfuric acid and the like.
Specifically, the acid is hydrochloric acid or a mixture of one or more of formic acid, acetic acid, propionic acid and lactic acid.
In a second aspect of the present disclosure, there is provided the use of the eutectic solvent of the first aspect in the extraction of lignin.
In a third aspect of the present disclosure, there is provided a method for extracting lignin, the method comprising extracting with the eutectic solvent of the first aspect.
Preferably, the extraction method comprises the following steps: and (2) performing benzyl alcohol extraction on the sample, adding the eutectic solvent in the first aspect into the extracted sample, mixing and heating to obtain a mixed solution, and obtaining a liquid part in the mixed solution to precipitate to obtain the lignin.
Further preferably, the sample is a wood product after extraction of benzene alcohol.
In some specific embodiments, the wood product is wood chips, wood flour, etc., which can be determined according to a specific process.
In some specific examples, the wood flour is prepared as follows: taking the wood chips with the length of 15-25 mm, the width of 10-20 mm and the thickness of 3-5 mm, air-drying and crushing the wood chips, and then screening the wood powder with 40-60 meshes.
In some specific examples, the way of extracting the benzene alcohol is: placing the wood product into a mixed solution of benzene and ethanol with a volume ratio of 1:2, extracting for 6-8 h, and drying to constant weight.
Preferably, the extracted sample and the eutectic solvent are mixed according to the solid-to-liquid ratio of 1: 5-1: 50.
Preferably, the mixing and heating temperature is 60-180 ℃, and the heating and stirring are carried out for 4-36 hours.
Through a large number of experimental verifications and analyses, in order to obtain the best result, the solid-liquid ratio is 1:30, the reaction temperature is 140 ℃, and the reaction time is 12 hours.
Preferably, the extraction method further comprises a step of purifying the lignin, wherein the purification step comprises the following steps: and adding absolute ethyl alcohol into the mixed solution, performing suction filtration, washing the solid part to obtain filtrate and washing liquid, namely the liquid part, and standing to obtain precipitate, namely the lignin.
More preferably, water is added into the liquid part for standing, and the volume ratio of the liquid part to the water is 1: 2-1: 10.
Preferably, the washing liquid used in the washing process is an ethanol aqueous solution, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 1-1: 10.
The analytical methods used in the following examples are as follows:
the extraction rate of lignin is as follows:
x-the extraction rate of lignin%
m1-mass of lignin extracted by eutectic solvent treatment, g
m0Mass of the raw materials taken for pretreatment, g
Alpha-the content of lignin in the raw material%
Purity of lignin extracted by eutectic solvent:
x2-low co-solvent extraction of lignin purity%
m1-mass of lignin extracted by eutectic solvent treatment, g
m2-mass of acid-insoluble lignin in the lignin extracted by the eutectic solvent, g
m3-mass of acid-soluble lignin in the extraction of lignin from the eutectic solvent, g
The rest of the experimental methods which are not described in detail are all routine experimental methods in the field.
Example 1:
processing poplar raw materials by adopting a choline lactate-lactic acid eutectic solvent to extract lignin.
(1) Pretreatment of raw materials: taking relatively uniform wood chips, air-drying, crushing, and screening to obtain 40-60-mesh wood powder.
(2) Extracting benzene alcohol: and (3) performing benzene alcohol extraction on the wood powder by using a benzene-ethanol mixed solution with the volume ratio of 2:1, extracting for 6-8 h, drying and keeping the weight constant.
(3) Preparing a eutectic solvent: mixing choline chloride and potassium hydroxide according to the mass ratio of 1:1, heating and stirring for 4h at the reaction temperature of 60 ℃ in an ethanol solvent, filtering, retaining the supernatant, adding lactic acid according to the mass ratio of 1:1, carrying out rotary evaporation drying, mixing with lactic acid according to the mass ratio of 1:10, heating for 5h at the temperature of 60 ℃, and cooling to room temperature to obtain the choline lactate-lactic acid eutectic solvent.
(4) Eutectic solvent treatment: and (3) mixing the wood powder extracted in the step (2) with the eutectic solvent in the step (3), heating at the constant temperature of 140 ℃, and stirring for 12 hours to obtain a mixed solution.
(5) And (3) treating the mixture: and (4) carrying out suction filtration on the mixture obtained in the step (4), taking filtrate obtained by suction filtration, adding a large amount of deionized water, standing for precipitation, centrifuging, and washing to obtain the lignin.
As a result: through detection, the extraction rate of the lignin treated by the choline lactate-lactic acid eutectic solvent is 90.12%, the purity of the lignin is 90.84%, the molecular weight is 4084, and the polydispersity coefficient is 1.9. In contrast, the extraction rate of lignin by the eutectic solvent with normal halogen content (choline chloride-lactic acid) under the same condition is 78.00%, and the purity of lignin is 88.81%. The extraction rate of the modified low-halogen (choline lactate-lactic acid) eutectic solvent is improved by 12.12%, and the purity is improved by 2.03%.
Referring to line B of FIG. 1, the infrared spectrum of lignin prepared from the eutectic solvent of this example shows 3427cm-1Is the stretching vibration of hydroxyl on the lignin structure, 1326cm-1、1270cm-1、1216cm-1、1120cm-1Is a characteristic absorption peak of a lignin basic structural unit, 1513cm-1、1424cm-1Is the vibration of the aromatic ring skeleton of the lignin. The above characteristic vibration absorption peaks illustrate the comparison with the IR spectra of A-line groundwood lignin, prepared by eutectic solvents in this exampleThe lignin host structure is not destroyed.
Example 2:
treating poplar raw material by using choline formate-formic acid eutectic solvent to extract lignin.
(1) Pretreatment of raw materials: taking relatively uniform wood chips, air-drying, crushing, and screening to obtain 40-60-mesh wood powder.
(2) Extracting benzene alcohol: and (3) performing benzene alcohol extraction on the wood powder by using a benzene-ethanol mixed solution with the volume ratio of 2:1, extracting for 6-8 h, drying and keeping the weight constant.
(3) Preparing a eutectic solvent: mixing choline chloride and potassium hydroxide according to the mass ratio of 1:1, heating and stirring for 4h at the reaction temperature of 60 ℃ in an ethanol solvent, filtering, retaining the supernatant, adding formic acid according to the mass ratio of 1:1, carrying out rotary evaporation drying, mixing with formic acid according to the mass ratio of 1:10, heating for 5h at the temperature of 60 ℃, and cooling to room temperature to obtain the choline formate-formic acid eutectic solvent.
(4) Eutectic solvent treatment: and (3) mixing the wood powder extracted in the step (2) with the eutectic solvent in the step (3), heating at the constant temperature of 140 ℃, and stirring for 12 hours to obtain a mixed solution.
(5) And (3) treating the mixture: and (4) carrying out suction filtration on the mixture obtained in the step (4), taking filtrate obtained by suction filtration, adding a large amount of deionized water, standing for precipitation, centrifuging, and washing to obtain the lignin.
As a result: through detection, the extraction rate of the lignin treated by the choline formate-formic acid eutectic solvent is 91.43% and the purity of the lignin is 89.03%. In contrast, the normal halogen content (choline chloride-formic acid) eutectic solvent treated under the same conditions gave a lignin extraction rate of 85.65% and a lignin purity of 85.56%. The extraction rate of the modified low-halogen (choline lactate-formic acid) eutectic solvent is improved by 5.78%, and the purity is improved by 3.47%.
Referring to line C of FIG. 1, the infrared spectrum of lignin obtained from the eutectic solvent of this example shows 3427cm-1Is the stretching vibration of hydroxyl on the lignin structure, 1326cm-1、1270cm-1、1216cm-1、1120cm-1Is lignin basic structure sheetCharacteristic absorption Peak of Meta, 1513cm-1、1424cm-1Is the vibration of the aromatic ring skeleton of the lignin. The above characteristic vibration absorption peaks demonstrate that the lignin host structure produced by the eutectic solvent in this example is not destroyed, as compared to the infrared spectrum of a line groundwood lignin.
Example 3:
treating poplar raw material by adopting choline propionate-propionic acid eutectic solvent to extract lignin.
(1) Pretreatment of raw materials: taking relatively uniform wood chips, air-drying, crushing, and screening to obtain 40-60-mesh wood powder.
(2) Extracting benzene alcohol: and (3) performing benzene alcohol extraction on the wood powder by using a benzene-ethanol mixed solution with the volume ratio of 2:1, extracting for 6-8 h, drying and keeping the weight constant.
(3) Preparing a eutectic solvent: mixing choline chloride and potassium hydroxide according to the mass ratio of 1:1, heating and stirring for 4h at the reaction temperature of 60 ℃ in an ethanol solvent, filtering, retaining the supernatant, adding propionic acid according to the mass ratio of 1:1, carrying out rotary evaporation drying, mixing with propionic acid according to the mass ratio of 1:10, heating for 5h at the temperature of 60 ℃, and cooling to room temperature to obtain the choline propionate-propionic acid eutectic solvent.
(4) Eutectic solvent treatment: and (3) mixing the wood powder extracted in the step (2) with the eutectic solvent in the step (3), heating at the constant temperature of 140 ℃, and stirring for 12 hours to obtain a mixed solution.
(5) And (3) treating the mixture: and (4) carrying out suction filtration on the mixture obtained in the step (4), taking filtrate obtained by suction filtration, adding a large amount of deionized water, standing for precipitation, centrifuging, and washing to obtain the lignin.
As a result: through detection, the extraction rate of the lignin treated by the choline propionate-propionic acid eutectic solvent is 65.78%, and the purity of the lignin is 89.82%. In contrast, the normal halogen content (choline chloride-propionic acid) eutectic solvent treated under the same conditions gave a lignin extraction of 63.71% and a lignin purity of 86.90%. The extraction rate of the modified low-halogen (choline lactate-propionic acid) eutectic solvent is improved by 2.07%, and the purity is improved by 2.92%.
Referring to line D of FIG. 1, the eutectic solvent of this example was preparedThe obtained infrared spectrogram of lignin has a length of 3427cm-1Is the stretching vibration of hydroxyl on the lignin structure, 1326cm-1、1270cm-1、1216cm-1、1120cm-1Is a characteristic absorption peak of a lignin basic structural unit, 1513cm-1、1424cm-1Is the vibration of the aromatic ring skeleton of the lignin. The above characteristic vibration absorption peaks demonstrate that the lignin host structure produced by the eutectic solvent in this example is not destroyed, as compared to the infrared spectrum of a line groundwood lignin.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (11)
1. A method for extracting lignin, wherein the lignin is derived from poplar wood, and the method for extracting the lignin comprises the steps of extracting by using a eutectic solvent;
the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor and the hydrogen bond donor are mixed according to the amount of the substance of 1: 1-1: 20 and then are heated and stirred for 1-8 hours at the temperature of 30-80 ℃ to obtain the eutectic solvent;
the preparation method of the eutectic solvent hydrogen bond receptor comprises the following steps of mixing choline chloride and potassium hydroxide, adding the mixture into an alcohol solvent, heating, and taking a supernatant part; adding one of formic acid, acetic acid, propionic acid, butyric acid and lactic acid into the supernatant, and mixing to obtain a hydrogen bond receptor; the hydrogen bond donor is one of formic acid, acetic acid, propionic acid, butyric acid and lactic acid;
the extraction method comprises the following steps: and (3) performing benzyl alcohol extraction on the sample, adding the eutectic solvent into the extracted sample, mixing and heating to obtain a mixed solution, and obtaining a liquid part in the mixed solution to precipitate to obtain the lignin.
2. The method for extracting lignin according to claim 1, wherein the choline chloride and the potassium hydroxide are mixed in an amount of 1:1 to 1: 2.
3. The method for extracting lignin according to claim 1, wherein the alcoholic solvent is ethanol.
4. The method for extracting lignin according to claim 1, wherein one of formic acid, acetic acid, propionic acid, butyric acid and lactic acid is added to choline chloride and potassium hydroxide in an amount of 1:0.5 to 1: 5.
5. The method for extracting lignin according to claim 1, wherein the sample is a wood product after extraction with benzene alcohol;
the wood product is wood chip or wood powder; the preparation process of the wood powder is as follows: taking the wood chips with the length of 15-25 mm, the width of 10-20 mm and the thickness of 3-5 mm, air-drying and crushing the wood chips, and then screening the wood powder with 40-60 meshes.
6. The method for extracting lignin according to claim 5, wherein the extraction of the benzene alcohol is performed by: placing the wood product into a mixed solution of benzene and ethanol with a volume ratio of 1:2, extracting for 6-8 h, and drying to constant weight.
7. The method for extracting the lignin according to claim 1, wherein the extracted sample is mixed with a eutectic solvent according to a solid-to-liquid ratio of 1: 5-1: 50; the mixing and heating temperature is 60-180 ℃, and the heating and stirring are carried out for 4-36 hours.
8. The method for extracting lignin according to claim 7, wherein the solid-to-liquid ratio is 1:30, the reaction temperature is 140 ℃, and the reaction time is 12 h.
9. The method for extracting lignin according to claim 1, further comprising the step of purifying lignin, wherein the step of purifying lignin comprises: adding absolute ethyl alcohol into the mixed solution, carrying out suction filtration, washing the solid part to obtain filtrate and washing liquid, namely the liquid part, adding water, standing to obtain precipitate, namely the lignin.
10. The method for extracting lignin according to claim 9, wherein the liquid fraction is added with water and allowed to stand, and the volume ratio of the liquid fraction to water is 1:2 to 1: 10.
11. The method for extracting the lignin according to claim 9, wherein a washing liquid adopted in the washing process is an ethanol aqueous solution, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 1-1: 10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910813666.1A CN110540508B (en) | 2019-08-30 | 2019-08-30 | Eutectic solvent and application thereof in extracting lignin |
| KR1020217017261A KR20210088650A (en) | 2019-08-30 | 2020-01-03 | Eutectic solvents and their applications in lignin extraction |
| PCT/CN2020/070222 WO2021036156A1 (en) | 2019-08-30 | 2020-01-03 | Eutectic solvent and application thereof in extracting lignin |
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| CN108660837B (en) * | 2018-05-29 | 2021-03-30 | 南京林业大学 | Method for separating cellulose, hemicellulose and lignin from plant fiber raw material |
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| CN110540508A (en) | 2019-12-06 |
| WO2021036156A1 (en) | 2021-03-04 |
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