CN110804893B - Method for separating holocellulose in wood fibers by using choline eutectic solvent - Google Patents
Method for separating holocellulose in wood fibers by using choline eutectic solvent Download PDFInfo
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- CN110804893B CN110804893B CN201911122037.0A CN201911122037A CN110804893B CN 110804893 B CN110804893 B CN 110804893B CN 201911122037 A CN201911122037 A CN 201911122037A CN 110804893 B CN110804893 B CN 110804893B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
Abstract
The invention relates to a method for separating holocellulose in wood fibers by using a choline eutectic solvent, which comprises the following steps: the method comprises the steps of raw material pretreatment, benzene alcohol extraction, eutectic solvent preparation, eutectic solvent treatment, holocellulose separation and solvent recovery. The method is characterized in that chloride ions in choline eutectic solvent are replaced under mild conditions, and nontoxic hydrogen bond donors are matched to prepare the eutectic solvent with low halogen content, and the eutectic solvent is used for separating holocellulose in wood fibers. The method has the advantages of high extraction rate of holocellulose, high purity, simple operation, obvious effect, strong practicability, little pollution and easy popularization.
Description
Technical Field
The invention belongs to the technical field of biomass refining, and particularly relates to a choline eutectic solvent and application of the solvent system in extraction and separation of holocellulose.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention 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.
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 wood fiber, can realize the dissolution of all components of the wood fiber, and sequentially dissolves out cellulose and lignin components by adding a precipitator.
At present, the research mainly adopts a choline chloride eutectic solvent, choline chloride is used as a hydrogen bond receptor, various organic acids, urea and the like are used as hydrogen bond donors, and the eutectic solvent has strong fiber dissolving capacity and good lignin purification effect. However, due to the existence of chloride ions, negative charges are distributed too intensively, interaction between the eutectic solvent and fibers is not facilitated, and meanwhile, corrosion of instruments and equipment aging are caused in the using process.
Disclosure of Invention
In order to overcome the problems and effectively separate and extract the wood fiber component, the invention provides a method for modifying the choline eutectic solvent and using the modified choline eutectic solvent for separating and extracting the wood fiber component.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a choline eutectic solvent comprises the following steps:
mixing choline chloride and an alkaline substance, dispersing in an alcohol solvent, heating and stirring at the reaction temperature of 20-80 ℃ for 1-8 h, filtering, retaining the supernatant, adding an acid, and drying to obtain a hydrogen bond receptor;
heating and uniformly mixing the hydrogen bond acceptor and the hydrogen bond donor to obtain the eutectic solvent.
The alkaline substance is at least one of sodium hydroxide and potassium hydroxide.
The alcohol solvent is one or the mixture of methanol and ethanol.
According to the method, organic acid radical ions are used for replacing chloride ions in the choline eutectic solvent, the halogen content of the eutectic solvent is reduced, the dissolving and separating effects of wood fibers are effectively improved, the extraction efficiency and purity of holocellulose are improved, and the equipment loss is reduced.
In some embodiments, the acid is hydrochloric acid or a mixture of one or more of formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycine, lysine, arginine, alanine, glutamic acid, and sulfuric acid. By replacing halogen anions in choline chloride with organic acid radical ions, the anion charge density of the eutectic solvent is dispersed, the dissolving efficiency of wood fibers is improved, and meanwhile, the holocellulose separation efficiency is improved through proper eutectic solvent type selection; 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 some embodiments, 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 and p-toluenesulfonic acid, so that the prepared eutectic solvent has strong fiber dissolving capacity and good lignin purification effect.
In some embodiments, the amount of the hydrogen bond acceptor and the hydrogen bond donor is 1: 1-1: 20, the reaction temperature is 30-80 ℃, and the reaction time is 1-8 hours, so as to improve the dissolution efficiency of wood fibers and the separation efficiency of holocellulose.
The invention also provides the choline eutectic solvent prepared by any one of the methods.
The invention also provides a method for separating holocellulose in wood fibers by using the choline eutectic solvent, which comprises the following steps:
mixing wood powder after the extraction of the benzene alcohol with the choline eutectic solvent, heating and stirring to obtain a mixed solution;
and (4) carrying out suction filtration on the mixed solution, collecting solid residues, washing and drying to obtain the holocellulose. Aiming at the problems of low extraction rate of holocellulose, poor separation effect, equipment corrosion and the like caused by high halogen content in the process of dissolving and separating plant fiber components by using a eutectic solvent, the invention provides a method for modifying the traditional choline eutectic solvent and using the modified choline eutectic solvent for separating and extracting the holocellulose in wood fibers. By replacing halogen anions in choline chloride with organic acid radical ions, the anion charge density is dispersed, and the efficiency and the effect of dissolving, separating and extracting the wood fibers are improved.
In some embodiments, the solid-to-liquid ratio of the wood powder to the eutectic solvent is 1: 15-1: 35, so that the wood powder is better dispersed in the eutectic solvent, and the mixing efficiency is improved.
In some embodiments, the solution is heated to 140-160 ℃, stirred for 12-14 h, the extraction rate of the holocellulose is improved, and the separation effect is improved.
The invention also provides the holocellulose prepared by any one of the methods.
The invention also provides the application of the holocellulose in the preparation of biomass fuel and bio-based products, wherein the bio-based products comprise: energy-saving heat-insulating material, thermosetting resin material and functional polymer material.
The invention has the beneficial effects that:
(1) the holocellulose obtained by the process disclosed by the invention is high in extraction rate, high in purity and small in structural damage degree, and the utilization value of the holocellulose 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 incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a FT-IR spectrum of the wood holocellulose extracted with the eutectic solvent in examples 1 to 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 application 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 application. 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.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
The invention provides a method for separating holocellulose in wood fibers by using a choline eutectic solvent, which comprises the following steps:
(1) pretreatment of raw materials: taking the wood chips, air drying, crushing and screening to obtain the wood powder.
Specifically, wood chips with the length of 15-25 mm, the width of 10-20 mm and the thickness of 3-5 mm which are relatively uniform are taken, air-dried, crushed and screened with 40-60 meshes of wood powder.
(2) Extracting benzene alcohol: and (3) performing benzyl alcohol extraction on the wood powder, drying and keeping constant weight to obtain the extracted wood powder.
Specifically, a benzene-ethanol mixed solution with a volume ratio of 2:1 is prepared, the wood powder is extracted for 6-8 hours, and the wood powder is dried and has constant weight.
(3) Preparing a eutectic solvent: and heating, stirring and mixing the hydrogen bond acceptor and the hydrogen bond donor of the eutectic solvent to obtain the eutectic solvent.
Specifically, the eutectic solvent is prepared by mixing a hydrogen bond acceptor and a hydrogen bond donor according to the amount of the substances of 1:10, and heating and stirring for 5 hours at the reaction temperature of 60 ℃.
Specifically, the hydrogen bond receptor is prepared by mixing choline chloride and potassium hydroxide according to the mass amount of 1: 1-1: 2, heating and stirring for 1-8 hours at the reaction temperature of 20-80 ℃ in an ethanol solvent, filtering, keeping a supernatant, adding acid according to the mass amount of 1: 0.5-1: 5, and performing rotary evaporation drying.
Specifically, the acid is hydrochloric acid or a mixture of one or more of formic acid, acetic acid, propionic acid and lactic acid.
(4) Eutectic solvent treatment: mixing the extracted wood powder with the eutectic solvent, heating at constant temperature, and stirring to obtain a mixed solution.
Specifically, the extracted wood flour obtained in the step (2) and the eutectic solvent obtained in the step (3) are mixed according to the solid-to-liquid ratio of 1:30, the reaction temperature is 140 ℃, and the mixture is heated and stirred for 12 hours.
(5) Separating holocellulose: and (3) carrying out suction filtration on the mixed solution, washing by using absolute ethyl alcohol, taking filter residue, washing by using deionized water, and drying to obtain the holocellulose.
And (3) adding absolute ethyl alcohol into the mixed solution obtained in the step (4), performing suction filtration and separation, washing the solid residue with ethyl alcohol and deionized water for 2-3 times, and drying to obtain the holocellulose.
(6) And (3) solvent recovery: and (4) after lignin is separated from the filtrate obtained in the step (5), performing rotary evaporation separation and drying to obtain a recovered eutectic solvent, and reusing the recovered eutectic solvent in the step (4) for treatment.
The analysis method adopted in the embodiment of the invention is as follows:
the yield of holocellulose is as follows:
X1yield of holocellulose
m1-mass of holocellulose obtained by treatment with eutectic solvent, g
m0Mass of the raw materials taken for pretreatment, g
Extraction rate of holocellulose:
X2extraction ratio of holocellulose
Alpha-content of holocellulose in the raw material%
Purity of holocellulose:
X3-the purity of the holocellulose,
m1-mass of holocellulose obtained by treatment with eutectic solvent, g
m2-treatment to obtain the cellulose content of the holocellulose, g
m3-treatment to obtain the content of hemicellulose in the holocellulose, g
The rest of the experimental methods which are not described in detail are all routine experimental methods in the field.
The principle of the invention is as follows: by replacing halogen anions in choline chloride with organic acid radical ions, the anion charge density of the eutectic solvent is dispersed, the dissolving efficiency of wood fibers is improved, and meanwhile, the holocellulose separation efficiency is improved through proper eutectic solvent type selection; 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.
Specifically, the present invention provides a method for separating lignocellulosic components using a choline-based eutectic solvent, comprising the steps of:
(1) pretreatment of raw materials: taking the wood chips, air drying, crushing and screening to obtain the wood powder.
(2) Extracting benzene alcohol: and (2) performing benzyl alcohol extraction on the wood powder obtained in the step (1), drying and keeping constant weight to obtain the extracted wood powder.
(3) Preparing a eutectic solvent: and heating, stirring and mixing the hydrogen bond acceptor and the hydrogen bond donor of the eutectic solvent to obtain the eutectic solvent.
(4) Eutectic solvent treatment: and (3) mixing the extracted wood powder obtained in the step (2) with the eutectic solvent obtained in the step (3), heating at constant temperature, and stirring to obtain a mixed solution.
(5) And (3) suction filtration: and (4) carrying out suction filtration, washing and separation on the mixed solution obtained in the step (4).
(6) Separating holocellulose: and (5) washing, separating and drying filter residues obtained after suction filtration in the step (5) to obtain the holocellulose.
(7) And (3) solvent recovery: and (4) delignifying the filtrate obtained in the step (6), performing rotary evaporation separation and drying to obtain the recovered eutectic solvent, and reusing the recovered eutectic solvent in the step (4) for treatment of the eutectic solvent.
Further, the pretreatment in the step (1) is specifically performed in the following manner: 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.
Further, the concrete way of the extraction of the benzene alcohol in the step (2) is as follows: and (2) placing the wood powder obtained by screening in the step (1) into a mixed solution of benzene and ethanol with the volume ratio of 1:2, extracting for 6-8 h, drying and keeping constant weight.
Further, the preparation method of the eutectic solvent in the preparation step of the eutectic solvent in the step (3) is specifically that a hydrogen bond acceptor and a hydrogen bond donor of the eutectic solvent are mixed according to the amount of the substances of 1: 1-1: 20, and the mixture is heated and stirred for 1-8 hours at the reaction temperature of 30-80 ℃ to obtain the eutectic solvent.
Further, the eutectic solvent in the step (3) of preparing the eutectic solvent specifically consists of a hydrogen bond acceptor and a hydrogen bond donor. Wherein, the hydrogen bond receptor is choline ionic liquid, and the structural formula is as follows:
wherein: the cation is choline cation; anion (X)-) Is one or more of chloride ion or formate, acetate, propionate, butyrate, lactate, glycinate, lysinate, arginate, alaninate, glutamate, hydrogen sulfate, etc.
Further, the hydrogen bond acceptor of the eutectic solvent in the step (3) of preparing the eutectic solvent is prepared in a specific manner as follows: the method comprises the steps of mixing choline chloride and potassium hydroxide according to the mass ratio of 1: 1-1: 2, heating and stirring for 1-8 hours at the reaction temperature of 20-80 ℃ in an ethanol solvent, filtering, keeping a supernatant, and adding one or more of hydrochloric acid or formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycine, lysine, arginine, alanine, glutamic acid, sulfuric acid and the like according to the mass ratio of 1: 0.5-1: 5 to obtain the hydrogen bond receptor.
Further, the hydrogen bond donor of the eutectic solvent in the step (3) of preparing the eutectic solvent is one or a mixture of several 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.
Further, the eutectic solvent treatment in the step (4) is specifically as follows: and (3) mixing the extracted wood powder obtained in the step (2) with a eutectic solvent according to a solid-to-liquid ratio of 1: 5-1: 50, reacting at the temperature of 60-180 ℃, and heating and stirring for 4-36 hours.
Further, the washing solution used in the washing in the step (5) is ethanol.
Further, the washing liquid level deionized water used for washing the filter residue in the step (6).
Preferably, the reaction conditions for preparing the low eutectic solvent in the step (3) are as follows: and mixing the hydrogen bond acceptor and the hydrogen bond donor according to the amount of the substances of 1: 1-1: 20, and heating and stirring for 1-8 hours at the reaction temperature of 30-80 ℃. After a large number of experimental verifications and analyses, in order to obtain the best result, the hydrogen bond acceptor and the hydrogen bond donor are mixed according to the amount of the substances of 1:10, and the mixture is heated and stirred for 5 hours at the reaction temperature of 60 ℃.
Preferably, the reaction conditions of the low eutectic solvent treatment in the step (4) are as follows: the solid-liquid ratio of the extracted wood powder to the eutectic solvent is 1: 5-1: 50, the reaction temperature is 60-180 ℃, and the reaction time is 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.
The design concept of the invention is as follows: the invention provides a method for modifying a traditional choline eutectic solvent and using the modified choline eutectic solvent to separate and extract holocellulose in wood fibers, aiming at the problems of low rate of extraction of holocellulose, poor separation effect, equipment corrosion and the like caused by high halogen content in the process of dissolving and separating plant fiber components by the eutectic solvent. By replacing halogen anions in choline chloride with organic acid radical ions, the anion charge density is dispersed, and the efficiency and the effect of dissolving, separating and extracting the wood fibers are improved.
Example 1:
treating poplar raw material by adopting choline lactate-lactic acid eutectic solvent to extract holocellulose.
(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 hours, drying and keeping constant weight.
(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 mixed solution obtained in the step (4), washing the solid residue obtained by suction filtration for 3 times by using ethanol and deionized water, and drying to obtain the holocellulose.
As a result: through detection, the yield of the holocellulose obtained by the treatment of the choline lactate-lactic acid eutectic solvent is 58.32%, the extraction rate is 75.08%, and the purity of the holocellulose is 92.60%. In contrast, the extraction rate of the holocellulose treated by the normal halogen content (choline chloride-lactic acid) eutectic solvent under the same condition is 62.64%, and the purity of the holocellulose is 89.42%. The extraction rate of the modified low-halogen content (choline lactate-lactic acid) eutectic solvent is improved by 12.44%, and the purity is improved by 3.18%.
Referring to line B in FIG. 1, 3427cm is an infrared spectrum of holocellulose prepared from the eutectic solvent of this example-1Stretching vibration of hydroxyl on holocellulose structure, 1427cm-1is-CH in cellulose2C-H deformation in (E) -1162 cm-1Is C-O-C symmetric stretching vibration in carbohydrate, 1058cm-1The C ═ O stretching vibration in carbohydrate. Compared with the raw material of line A, 1600cm in the holocellulose of eutectic solvent-1、1510cm-1、1270cm-1、1112cm-1And 835cm-1The area of the spectral peak is significantly reduced, which shows that most of the lignin in the poplar biomass feedstock is removed after treatment with the eutectic solvent in this example.
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 hours, drying and keeping constant weight.
(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 mixed solution obtained in the step (4), washing the solid residue obtained by suction filtration for 3 times by using ethanol and deionized water, and drying to obtain the holocellulose.
As a result: through detection, the yield of the holocellulose obtained by the choline formate-formic acid eutectic solvent treatment after the steps is detected to be 43.59%, the extraction rate is 56.12%, and the purity of the holocellulose is 90.25%. In contrast, the extraction rate of holocellulose treated by the eutectic solvent with normal halogen content (choline chloride-propionic acid) under the same condition is 62.52%, and the purity of the holocellulose is 87.44%. The extraction rate of the modified low-halogen content (choline lactate-lactic acid) eutectic solvent is reduced by 6.4%, and the purity is improved by 2.81%.
Referring to line C in FIG. 1, 3427cm is an infrared spectrum of holocellulose prepared from the eutectic solvent of this example-1Stretching vibration of hydroxyl on holocellulose structure, 1427cm-1is-CH in cellulose2C-H deformation in (E) -1162 cm-1Is C-O-C symmetric stretching vibration in carbohydrate, 1058cm-1The C ═ O stretching vibration in carbohydrate. Compared with the raw material of line A, 1600cm in the holocellulose of eutectic solvent-1、1510cm-1、1270cm-1、1112cm-1And 835cm-1The area of the spectral peak is significantly reduced, which shows that most of the lignin in the poplar biomass feedstock is removed after treatment with the eutectic solvent in this example.
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 hours, drying and keeping constant weight.
(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 mixed solution obtained in the step (4), washing the solid residue obtained by suction filtration for 3 times by using ethanol and deionized water, and drying to obtain the holocellulose.
As a result: through detection, the yield of the holocellulose obtained by the treatment of the choline propionate-propionic acid eutectic solvent after the treatment of the steps is 57.43%, the extraction rate is 73.98%, the purity of the holocellulose is 82.53%, the extraction rate of the holocellulose treated by the normal halogen content (choline chloride-propionic acid) eutectic solvent under the same conditions is 76.68%, and the purity of the holocellulose is 76.42%. The extraction rate of the modified low-halogen content (choline lactate-lactic acid) eutectic solvent is reduced by 2.7%, and the purity is improved by 6.11%.
Referring to line D in FIG. 1, 3427cm is an infrared spectrum of holocellulose prepared from the eutectic solvent of this example-1Stretching vibration of hydroxyl on holocellulose structure, 1427cm-1is-CH in cellulose2C-H deformation in (E) -1162 cm-1Is C-O-C symmetric stretching vibration in carbohydrate, 1058cm-1The C ═ O stretching vibration in carbohydrate. Compared with the raw material of line A, 1600cm in the holocellulose of eutectic solvent-1、1510cm-1、1270cm-1、1112cm-1And 835cm-1The area of the spectral peak is significantly reduced, which shows that most of the lignin in the poplar biomass feedstock is removed after treatment with the eutectic solvent in this example.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (7)
1. A method for separating holocellulose in wood fibers by using a choline eutectic solvent is characterized by comprising the following steps:
mixing wood powder after the extraction of the benzene alcohol with the choline eutectic solvent, heating and stirring to obtain a mixed solution;
carrying out suction filtration on the mixed solution, collecting solid residues, washing and drying to obtain holocellulose;
the preparation method of the choline eutectic solvent comprises the following steps:
mixing choline chloride and an alkaline substance, dispersing in an alcohol solvent, heating and stirring at the reaction temperature of 20-80 ℃ for 1-8 h, filtering, retaining the supernatant, adding an acid, and drying to obtain a hydrogen bond receptor; the alkaline substance is at least one of sodium hydroxide and potassium hydroxide; the alcohol solvent is one or the mixture of methanol and ethanol; the acid is one or a mixture of more of formic acid, acetic acid, propionic acid, butyric acid and lactic acid;
heating and uniformly mixing a hydrogen bond acceptor and a hydrogen bond donor to obtain a eutectic solvent; the hydrogen bond donor is one or a mixture of several of formic acid, acetic acid, propionic acid, butyric acid and lactic acid.
2. The method for separating holocellulose in wood fiber by using the choline eutectic solvent as claimed in claim 1, wherein the ratio of the amount of the substances of the hydrogen bond acceptor and the hydrogen bond donor is 1: 1-1: 20, and the reaction temperature is 30-80 ℃.
3. The method for separating holocellulose in wood fibers by using the choline eutectic solvent as claimed in claim 1, wherein the solid-to-liquid ratio of the wood powder to the eutectic solvent is 1: 30-35.
4. The method for separating holocellulose in wood fibers by using the choline eutectic solvent as claimed in claim 1, wherein the wood flour after the extraction of the benzene alcohol is mixed with the choline eutectic solvent, heated to 140-160 ℃, and stirred for 12-14 h.
5. Holocellulose prepared by the method of any one of claims 1 to 4.
6. Use of the holocellulose of claim 5 for the preparation of bio-based products, characterized in that said bio-based products comprise: biomass fuel, energy-saving heat-insulating material and functional polymer material.
7. Use of the holocellulose of claim 6 for the preparation of bio-based products, characterized in that said functional polymeric material is a thermosetting resin material.
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