CN116770612A - Method for efficiently separating lignin by using eutectic solvent and product - Google Patents
Method for efficiently separating lignin by using eutectic solvent and product Download PDFInfo
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- 239000006184 cosolvent Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
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Abstract
The application discloses a method and a product for efficiently separating lignin by using a eutectic solvent, which belong to the technical field of comprehensive utilization of biomass resources and comprise the following steps: the biomass raw material is pretreated, mixed with the eutectic solvent, heated and reacted, and then subjected to suction filtration, washing and drying to obtain the DES-holocellulose. The application also discloses the DES-holocellulose prepared by the preparation method. The application optimizes the reaction condition and the reaction time to realize the effect of separating lignocellulose from the eutectic solvent, realizes the efficient utilization of lignin, utilizes the eutectic solvent as the solvent to decompose lignin, can be reused after the eutectic solvent is recovered, and has the advantages of simple process, low cost and the like.
Description
Technical Field
The application belongs to the technical field of comprehensive utilization of biomass resources, and particularly relates to a method and a product for efficiently separating lignin by using a eutectic solvent.
Background
Lignocellulose biomass is taken as the most abundant renewable resource in the world, and the effective utilization of lignocellulose biomass has important significance for replacing non-renewable fossil energy, coping with energy crisis problems, reducing environmental pollution and accelerating structural transformation. In order to fully utilize the lignocellulose biomass, and convert the lignocellulose biomass into effectively utilized energy and chemicals, component separation is required for the lignocellulose biomass, which is also a difficulty in the field of biomass research. The lignocellulose component separating method mainly comprises the following steps: dilute acid, alkaline, steam explosion, high temperature liquid water, ammonia explosion, biological, organic solvent, ionic liquid, eutectic solvent, less used machinery, extrusion, etc. Ionic liquids, organic solvents, and eutectic solvents are currently emerging research hotspots.
Abbott et al first found in 2003 that the eutectic compound formed by the quaternary ammonium salt and the amide compound was named eutectic solvent (Deep Eutectic Solvents, DES). Through researches, the DES not only has similar physical and chemical properties as the ionic liquid, but also has low price, no toxicity, biodegradability and easy preparation and recovery, and is a novel green solvent. DES is a eutectic consisting essentially of a hydrogen bond acceptor and a hydrogen bond donor, which are connected to each other by hydrogen bonding. Typically formed of two or three components, having melting points lower than any of the individual components. Compared with the traditional ionic liquid preparation, the eutectic solvent has the advantages of simple preparation method, readily available materials and no need of purification after synthesis. The method for separating lignocellulose raw material by the eutectic solvent is simple and environment-friendly, and the repeatability of the eutectic solvent makes future industrialized application of the method possible.
Therefore, how to provide a method for efficiently separating lignin by using eutectic solvents and simultaneously obtaining DES-palm cellulose is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for efficiently separating lignin by using a eutectic solvent and a product thereof.
In order to achieve the above purpose, the present application provides the following technical solutions:
a method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
the biomass raw material is pretreated, mixed with the eutectic solvent, heated and reacted, and then subjected to suction filtration, washing and drying to obtain the DES-holocellulose.
Preferably, the pretreatment comprises the steps of:
pulverizing biomass raw materials, sieving with a 60-mesh sieve, extracting with a benzene-alcohol mixed solution in a Soxhlet extractor for 6h, and finally baking at 105 ℃ for 12h, and sealing and storing for later use.
The benzene alcohol solution is prepared from toluene and absolute ethyl alcohol according to a volume ratio of 2:1, mixing to obtain the product;
the biomass raw materials comprise wheat straw, rice husk, peanut shell and pine wood.
Preferably, the eutectic solvent includes a hydrogen bond acceptor and a hydrogen bond donor;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: (2-10).
Preferably, the hydrogen bond acceptor is choline chloride;
the hydrogen bond donor comprises one or any of lactic acid, oxalic acid, formic acid and urea;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:2;
or alternatively, the first and second heat exchangers may be,
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:10.
preferably, the preparation method of the eutectic solvent comprises the following steps:
and mixing the hydrogen bond donor with the hydrogen bond acceptor, and stirring and heating in a water bath until a uniform transparent solution is obtained, thus obtaining the low-cosolvent.
Preferably, the heating temperature is 90 ℃ and the time is 0.5h;
the stirring rate was 250r/min.
Preferably, the heating reaction temperature is 80-140 ℃ and the time is 2-18h.
Preferably, the heating reaction temperature is 120 ℃ and the time is 4 hours;
or alternatively, the first and second heat exchangers may be,
the heating reaction temperature is 120 ℃ and the time is 12 hours;
or alternatively, the first and second heat exchangers may be,
the heating reaction temperature is 120 ℃ and the time is 16h.
A DES-holocellulose prepared by a method for efficiently separating lignin by using eutectic solvent.
Compared with the prior art, the eutectic solvent used in the method consists of common choline and organic acid, has low cost, stable property, good environment and simple operation, can degrade hemicellulose in lignocellulose into oligosaccharide under mild conditions, has little loss of lignin and cellulose in the process, effectively avoids lignin condensation, and reduces the problems of environmental pollution, excessive energy consumption and the like to a certain extent. The application optimizes the reaction condition and the reaction time to the effect of separating lignocellulose from the eutectic solvent, realizes the high-efficiency utilization of lignin, and utilizes the eutectic solvent as the solvent to decompose lignin, thereby having the advantages of simple process, low cost and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is an infrared spectrum of DES-holocellulose obtained in examples 2-4 with pine stock.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order that the above-recited objects, features and advantages of the present application will become more readily apparent, a more particular description of the application will be rendered by reference to the appended drawings and appended detailed description.
The raw materials in the application are all purchased through a commercial way.
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
the biomass raw material is pretreated, mixed with the eutectic solvent, heated and reacted, and then subjected to suction filtration, washing and drying to obtain the DES-holocellulose.
Further, the preprocessing comprises the following steps:
pulverizing biomass raw materials, sieving with a 60-mesh sieve, extracting with a benzene-alcohol mixed solution in a Soxhlet extractor for 6h, and finally baking at 105 ℃ for 12h, and sealing and storing for later use.
The benzene alcohol solution is prepared from toluene and absolute ethyl alcohol according to a volume ratio of 2:1, mixing to obtain the product;
the biomass raw materials comprise wheat straw, rice husk, peanut shell and pine wood.
Further, the eutectic solvent includes a hydrogen bond acceptor and a hydrogen bond donor;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: (2-10).
Further, the hydrogen bond acceptor is choline chloride;
the hydrogen bond donor comprises one or any of lactic acid, oxalic acid, formic acid and urea;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:2;
or alternatively, the first and second heat exchangers may be,
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:10.
further, the preparation method of the eutectic solvent comprises the following steps:
and mixing the hydrogen bond donor with the hydrogen bond acceptor, and stirring and heating in a water bath until a uniform transparent solution is obtained, thus obtaining the low-cosolvent.
Further, the heating temperature is 90 ℃ and the time is 0.5h;
the stirring rate was 250r/min.
Further, the heating reaction temperature is 80-140 ℃ and the time is 2-18h.
Further, the heating reaction temperature is 120 ℃ and the time is 4 hours;
or alternatively, the first and second heat exchangers may be,
the heating reaction temperature is 120 ℃ and the time is 12 hours;
or alternatively, the first and second heat exchangers may be,
the heating reaction temperature is 120 ℃ and the time is 16h.
A DES-holocellulose prepared by a method for efficiently separating lignin by using eutectic solvent.
In order to make the technical solution of the present application more clearly understood, the following examples will be used for specific description.
In the embodiment of the application, the biomass raw material is pine powder.
The cellulose, hemicellulose and lignin content of the biomass was measured:
(1) Weighing 0.3g of dry biomass raw material, putting the dry biomass raw material into a 100mL pressure-resistant hydrolysis bottle, adding 3.0mL of prepared 72% sulfuric acid, uniformly mixing, carrying out hydrolysis reaction for 1h in a constant-temperature magnetic stirring water bath, wherein the temperature of the water bath is 30 ℃, and stirring and mixing by using a glass rod during the water bath, so that the sulfuric acid and a sample in a test tube can be fully mixed and hydrolyzed.
(2) Adding 84mL of deionized water into each pressure-resistant hydrolysis bottle, putting the hydrolysis bottles into a portable pressure steam sterilization pot, sterilizing for 1h at 121 ℃, carrying out suction filtration on the reaction mixture by using a dried G3 sand core funnel, collecting hydrolysis liquid, washing to be neutral by deionized water, putting into a 105 ℃ oven for drying to be constant weight, and weighing the quality of filter residues.
(3) Burning the filter residues in a muffle furnace at 575 ℃ for 6 hours, drying, cooling to room temperature, weighing, and calculating the mass of lignin and ash;
the glucose and xylose contents were measured by HPLC and used to calculate the cellulose content and hemicellulose content, respectively, in the biomass.
Three experiments were repeated for each sample and the average was taken.
The components of the pretreated pine used in the examples of the present application were measured by the above-described detection method as shown in the following table.
| Raw materials | Cellulose/% | Hemicellulose/% | Lignin/% | Ash/% |
| Extracting pine wood | 35.19 | 15.17 | 28.49 | 0.45 |
Example 1
Pretreatment of biomass raw materials:
pulverizing pine wood raw materials, sieving with a 60-mesh sieve, extracting with a benzene-alcohol mixed solution (toluene and absolute ethyl alcohol are mixed according to a volume ratio of 2:1) in a Soxhlet extractor for 6 hours, and finally drying at 105 ℃ for 12 hours, and sealing and storing for later use to obtain pretreated pine wood powder.
Example 2
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
(1) Choline chloride and urea are mixed according to a mole ratio of 1:10, preparing, adding a flask, mixing, heating and stirring in a water bath kettle at 90 ℃ for 0.5h until the mixture is fully dissolved to form uniform transparent solution, and cooling to obtain a eutectic solvent;
(2) The pretreated pine powder and the eutectic solvent are mixed according to the following ratio of 1:20, stirring for 12 hours at 120 ℃ under heating, filtering while the mixture is hot, collecting solids, washing the solids with absolute ethyl alcohol and deionized water for 3-4 times, and drying to obtain the DES-holocellulose.
Example 3
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
(1) Choline chloride and lactic acid are mixed according to a mole ratio of 1:10, adding the mixture into a flask, mixing, heating and stirring in a water bath kettle at 90 ℃ for 0.5h until the mixture is fully dissolved to form uniform transparent solution, and cooling to obtain a low-cosolvent;
(2) The pine powder after suction filtration and the eutectic solvent are mixed according to the following ratio of 1:20, stirring for 16h at 120 ℃ under heating, filtering while hot, collecting solid, washing the solid with absolute ethanol and deionized water for 3-4 times, and drying to obtain the DES-holocellulose.
Example 4
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
(1) Choline chloride and lactic acid are mixed according to a mole ratio of 1:10, adding the mixture into a flask, mixing, heating and stirring in a water bath kettle at 90 ℃ for 0.5h until the mixture is fully dissolved to form uniform transparent solution, and cooling to obtain the low-cosolvent.
(2) The pine powder after suction filtration and the eutectic solvent are mixed according to the following ratio of 1:20, stirring for 12 hours at 120 ℃ under heating, filtering while the mixture is hot, collecting solids, washing the solids with absolute ethyl alcohol and deionized water, and drying to obtain the DES-holocellulose.
Example 5
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
(1) And (3) preparing choline chloride and lactic acid according to a molar ratio of 1:10, adding the mixture into a flask, mixing, heating and stirring the mixture in a water bath kettle at 90 ℃ for 0.5h until the mixture is fully dissolved to form uniform and transparent solution, and cooling the solution to obtain the low-cosolvent.
(2) Adding the pine powder subjected to suction filtration and the eutectic solvent into a liner of a reaction kettle according to a mass ratio of 1:20, stirring for 4 hours at 120 ℃, filtering while the mixture is hot, collecting solids, washing the solids with absolute ethyl alcohol and deionized water successively, and drying to obtain the DES-holocellulose.
Example 6
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
(1) And (3) preparing choline chloride and formic acid according to a molar ratio of 1:2, adding the choline chloride and the formic acid into a flask, mixing, heating and stirring in a water bath kettle at 90 ℃ for 0.5h until the choline chloride and the formic acid are fully dissolved to form uniform transparent solution, and cooling to obtain the low-cosolvent.
(2) Adding the pine powder subjected to suction filtration and the eutectic solvent into a liner of a reaction kettle according to a mass ratio of 1:20, stirring for 12 hours at 120 ℃, filtering while the mixture is hot, collecting solids, washing the solids with absolute ethyl alcohol and deionized water successively, and drying to obtain the DES-holocellulose.
Example 7
A method for efficiently separating lignin by using a eutectic solvent, comprising the following steps:
(1) And (3) preparing choline chloride and oxalic acid according to a molar ratio of 1:2, adding the mixture into a flask, mixing, heating and stirring the mixture in a water bath kettle at 90 ℃ for 0.5h until the mixture is fully dissolved to form uniform and transparent solution, and cooling the solution to obtain the low-cosolvent solvent.
(2) Adding the pine powder subjected to suction filtration and the eutectic solvent into a liner of a reaction kettle according to a mass ratio of 1:20, stirring for 12 hours at 120 ℃, filtering while the mixture is hot, collecting solids, washing the solids with absolute ethyl alcohol and deionized water successively, and drying to obtain the DES-holocellulose.
The technical effects are as follows:
the evaluation index calculation method of the embodiment of the application comprises the following steps:
yield of pine solids:
cellulose retention:
lignin removal rate:
hemicellulose retention:
X get yield of pine solids,%;
Y cont retention of cellulose,%;
Z dis lignin removal rate,%;
P dis retention of hemicellulose,%;
m 1 DES-holocellulose mass, g;
m 0 the mass of pine wood raw material before reaction, g;
a 0 cellulose content in pine wood raw material,%;
a 1 cellulose content in DES-holocellulose,%;
b 0 lignin content in pine raw material,%;
b 1 lignin content,%;
c 0 hemicellulose content in pine wood raw material,%;
c 1 hemicellulose content in DES-holocellulose,%.
The evaluation results of examples 2 to 7 are shown in Table 1:
TABLE 1
Table 1 shows the results of the lignin removal, solids yield and hemicellulose retention therein obtained by the measurements and calculations performed in examples 2-7 above. It can be seen that different reaction conditions produce different separation effects, which are mainly manifested in that the effect is better when the hydrogen bond donor is an acidic solution, and the longer the reaction time is, the better the effect is.
The DES-holocellulose obtained in examples 2-4 and pine material were subjected to infrared spectroscopic examination, and the results are shown in FIG. 1, which shows that the spectrum is 3400-3330cm -1 The Jiang Kuan peak at which is mainly the alcoholic hydroxyl group O-H stretching vibration, the stretching indicates the intractable untangling of the cellulose after pretreatment. Example 4, example 3 at 2937cm -1 Absorption peaks appear at the sites, mainly C-H stretching vibration of cellulose methyl and methylene. Example 4, example 3 at 1741cm -1 The enhancement of the absorption peak, where the absorption peak of example 2 disappeared, indicates that hemicellulose was degraded in example 2 and that the ChCl-Ua system (i.e. the eutectic solvent obtained in example 2) gave better hemicellulose removal. 1657cm -1 For the conjugated carbonyl absorbance peak in lignin, example 4 where the absorbance peak disappeared, example 3 where the absorbance peak was weakened, and example 2 where the absorbance peak was still evident. At 1606cm -1 、1509cm -1 、1427cm -1 The absorption peaks are aromatic skeleton C-C vibration peaks, and the absorption peaks in the examples 4 and 3 are weakened, and a certain amount of lignin is removed from the pretreated substrate biomass; example 2 the absorption peak is evident here, the benzene ring structure in lignin is still present. 1370cm -1 、1157cm -1 The C-H bending vibration peak at this point is a characteristic peak of xylan. At 1325cm -1 、1220cm -1 、1120cm -1 The C-O absorption peak of syringyl (S) did not appear, indicating that the DES-holocellulose building block separated from the pine stock did not contain syringyl or contained less. Furthermore, 1270cm -1 Is predominantly the specific C-O, C-O, C =o stretching vibration of guaiacyl (G) in lignin structures, which is predominantly lignin present in cork. Example 4, example 3 at 1270cm -1 The reduction of the peak indicates that the eutectic solvent pretreatment in the present application can reduce lignin content.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (9)
1. A method for efficiently separating lignin by using a eutectic solvent, which is characterized by comprising the following steps:
the biomass raw material is pretreated, mixed with the eutectic solvent, heated and reacted, and then subjected to suction filtration, washing and drying to obtain the DES-holocellulose.
2. A method for efficiently separating lignin using a eutectic solvent according to claim 1 wherein the pretreatment comprises the steps of:
pulverizing biomass raw materials, sieving with a 60-mesh sieve, extracting with a benzene-alcohol mixed solution in a Soxhlet extractor for 6 hours, and finally baking at 105 ℃ for 12 hours, and sealing and storing for later use;
the benzene alcohol solution is prepared from toluene and absolute ethyl alcohol according to a volume ratio of 2:1, mixing to obtain the product;
the biomass raw materials comprise wheat straw, rice husk, peanut shell and pine wood.
3. The method for efficiently separating lignin using a eutectic solvent according to claim 1, wherein the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: (2-10).
4. A method for efficiently separating lignin using a eutectic solvent according to claim 3 wherein the hydrogen bond acceptor is choline chloride;
the hydrogen bond donor comprises one or any of lactic acid, oxalic acid, formic acid and urea;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:2.
5. a method for efficiently separating lignin using a eutectic solvent according to claim 3 or 4, wherein the method for preparing the eutectic solvent comprises the steps of:
and mixing the hydrogen bond donor with the hydrogen bond acceptor, and stirring and heating in a water bath until a uniform transparent solution is obtained, thus obtaining the low-cosolvent.
6. The method for efficiently separating lignin using a eutectic solvent according to claim 5 wherein the heating temperature is 90 ℃ for 0.5h;
the stirring speed is 250r/min;
the washing is to wash with the eutectic solvent and then wash with water.
7. The method for efficiently separating lignin using a eutectic solvent according to claim 1, wherein the heating reaction temperature is 80-140 ℃ for 2-18 hours.
8. The method for efficiently separating lignin using a eutectic solvent according to claim 7, wherein the heating reaction temperature is 120 ℃ for 4 hours;
or alternatively, the first and second heat exchangers may be,
the heating reaction temperature is 120 ℃ and the time is 12 hours;
or alternatively, the first and second heat exchangers may be,
the heating reaction temperature is 120 ℃ and the time is 16h.
9. The DES-holocellulose prepared by a method for efficiently separating lignin using a eutectic solvent according to claim 1.
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