CN109162137B - Microcrystalline cellulose and method for preparing microcrystalline cellulose by using crop straws - Google Patents
Microcrystalline cellulose and method for preparing microcrystalline cellulose by using crop straws Download PDFInfo
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- CN109162137B CN109162137B CN201811116221.XA CN201811116221A CN109162137B CN 109162137 B CN109162137 B CN 109162137B CN 201811116221 A CN201811116221 A CN 201811116221A CN 109162137 B CN109162137 B CN 109162137B
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- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
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Abstract
The invention discloses microcrystalline cellulose and a method for preparing the microcrystalline cellulose by using crop straws. Separating and extracting straw crude cellulose by adopting a high-boiling-point organic solvent, partially hydrolyzing the obtained crude cellulose under the action of a spherical solid acid catalyst, standing, filtering, collecting solids, and drying the obtained hydrolysis mixed solution to obtain a solid mixture of the spherical solid acid catalyst and microcrystalline cellulose, and further screening to recover the solid catalyst to obtain the microcrystalline cellulose, wherein the polymerization degree is between 156 and 402. The microcrystalline cellulose prepared by the invention has high purity and moderate polymerization degree, can be used as a fine chemical raw material, the adopted high-boiling-point solvent has low volatility and good thermal stability, and can be recovered through simple extraction operation, the adopted solid acid catalyst has high catalytic activity and is easy to separate and recover, and the problems of pollution and corrosion caused by the fact that the low-boiling-point solvent is easy to volatilize and inorganic strong acid is used in the traditional method are solved.
Description
Technical Field
The invention belongs to the field of resources and environment, particularly relates to high-value utilization of agricultural waste resources, and more particularly relates to microcrystalline cellulose and a method for preparing microcrystalline cellulose by using crop straws.
Background
Crop straws are a precious renewable biomass resource, and according to the report of the environmental planning agency of the United nations, crops planted in the world can provide about 20 hundred million tons of straws every year. The Chinese straw yield is at the first position in the world, about 7 hundred million tons of straws are produced every year, and the Chinese straw yield can be folded into 3.53 million tons of standard coal. With the continuous deterioration of the environment and the increasing shortage of fossil resources and wood resources, the development of comprehensive utilization of renewable resources has become one of the effective ways to cope with the current resource shortage.
The straw is complex in structure and composition and mainly comprises three components of cellulose, hemicellulose and lignin, wherein the structure of the cellulose is simplest and the content of the cellulose in the straw is highest. The cellulose is polymerized by glucose units, can be directly converted into modified cellulose or hydrolyzed into D-glucose, and then further converted into other fine chemicals, and can be used for preparing chemical products with wide application, such as microcrystalline cellulose, glucose, cellulose acetate, 5-hydroxymethylfurfural and the like. Wherein the microcrystalline cellulose can be partially depolymerized from natural cellulose (alpha-cellulose), the degree of polymerization is reduced, and the microcrystalline cellulose has lower degree of polymerization and higher specific surface area, so the microcrystalline cellulose is widely applied to the industries of medicine, food, cosmetics and light chemical industry; in addition, compared with alpha-cellulose, microcrystalline cellulose has higher reaction performance in the processes of carboxymethylation, acetylation and esterification, and is an important fine chemical raw material.
Domestic cellulose is mainly derived from cotton pulp and wood pulp, which are relatively expensive, and 80% of wood pulp is imported. In recent years, research workers at home and abroad develop and research the separation, extraction and purification technology of straw cellulose aiming at the characteristic of high content of straw cellulose. The crude cellulose of straws is separated and extracted by adopting a mixed solution of an organic solvent and water, and then the alpha-cellulose is hydrolyzed to the limit polymerization degree under the condition of controlling hydrolysis by dilute acid, so that the microcrystalline cellulose can be formed. At present, ethanol is the most widely applied organic solvent, and because ethanol and water form an azeotrope, a large amount of energy is consumed for recovering ethanol; and the boiling point of the ethanol is lower, and the ethanol is easy to volatilize in the treatment process. In addition, alpha-cellulose is usually partially hydrolyzed under the homogeneous catalysis of inorganic strong acids such as hydrochloric acid and sulfuric acid, the corrosivity and the waste liquid amount are large, the pollution is serious, the post-treatment cost is high due to the factors, the further large-scale deep processing and conversion utilization are not facilitated, and a method for preparing microcrystalline cellulose by cleanly utilizing crop straw cellulose is needed.
Disclosure of Invention
The invention aims to solve the problems, adopts a high-boiling-point organic solvent to pretreat the straws, reduces the volatilization of the organic solvent in the treatment process, and simultaneously adopts simple extraction operation to recover the organic solvent, thereby reducing the recovery cost.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing microcrystalline cellulose from crop straws, the method comprising:
(1) mixing straw powder, a mixed solvent and sulfuric acid, heating and stirring, and then cooling, centrifuging and filtering to obtain a filtrate and a solid product; the mixed solvent is a mixture of a high-boiling-point organic solvent and water;
(2) washing the solid product by using the mixed solvent same as the mixed solvent in the step (1), combining the filtrate with the mixed solvent, and extracting and recovering the high-boiling-point organic solvent to obtain the straw crude cellulose;
(3) mixing the straw crude cellulose with a weak base solution, heating and stirring, and then cooling, filtering and drying to obtain straw cellulose;
(4) mixing straw cellulose with a solid acid catalyst and water, heating, stirring, hydrolyzing, cooling, adding cold water with the temperature of 4-6 ℃, standing, filtering, washing the obtained solid substance to be neutral, drying, sieving, separating and recovering the catalyst to obtain the straw microcrystalline cellulose.
As a preferred embodiment of the invention, in the step (1), the weight ratio of the straw powder to the mixed solvent is 1: 4-12; the concentration of the sulfuric acid in the mixed solvent is 0.03-0.05M; in the mixed solvent, the volume ratio of the high-boiling-point organic solvent to water is 1-9: 1-4, and the most preferable ratio is 1: 1;
in the step (3), the weight ratio of the straw crude cellulose to the weak alkali solution is 1: 4-10, and the most preferable weight ratio is 1: 7.5;
in the step (4), the mass ratio of the solid acid catalyst to the straw cellulose is 1: 1-20, and the most preferable ratio is 1: 2.
According to the present invention, the stalks include, but are not limited to, at least one of wheat stalks, rice stalks, corn stalks, sorghum stalks and rape stalks.
As a preferable embodiment of the invention, the straw powder is obtained by crushing straws, and the particle size of the straw powder is less than or equal to 40 meshes.
As a preferred embodiment of the present invention, the high boiling point organic solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, γ -valerolactone, ethylene glycol, dimethylacetamide and dimethylsulfoxide.
In a preferred embodiment of the present invention, in step (2), the high-boiling organic solvent is recovered by extraction with at least one extractant selected from the group consisting of chloroform, ethyl acetate and petroleum ether, and most preferably chloroform.
In a preferred embodiment of the present invention, in the step (3),
the weak base solution is hydrogen peroxide solution and/or sodium carbonate solution;
preferably, the weak base solution is a mixture of hydrogen peroxide solution and sodium carbonate solution, the concentration of hydrogen peroxide in the mixture is 0.5-3 wt%, most preferably 2 wt%, and the concentration of sodium carbonate is 1-10 wt%, most preferably 6 wt%.
In a preferred embodiment of the present invention, in the step (4), the solid acid catalyst is spherical particles having a particle size of 300 to 1000 μm. More preferably, the solid acid catalyst is Amberlyst 15, Amberlyst 35, Amberlyst 36, Amberlyst 45, Amberlite IR120H, D001, D002, D072H, or NKC-9, most preferably Amberlyst 45.
As a preferred embodiment of the present invention,
in the step (1), the heating and stirring temperature is 150-210 ℃, the most preferable temperature is 190 ℃, and the time is 2-10 hours, the most preferable time is 6 hours;
in the step (3), the heating and stirring temperature is 30-90 ℃, the most preferable temperature is 60 ℃, and the time is 1-20 hours, the most preferable time is 7 hours;
in the step (4), the hydrolysis temperature is 50-95 ℃, the most preferable temperature is 80 ℃, and the hydrolysis time is 0.5-6 h, the most preferable time is 2 h.
In the step (3) and the step (4), the drying temperature is 30-60 ℃ and the drying time is 8-12 hours.
In the present invention, the water may be experimental water conventionally used by those skilled in the art, including but not limited to ultrapure water, pure water, distilled water, deionized water.
A second aspect of the invention provides microcrystalline cellulose obtainable by the above process.
According to the present invention, the microcrystalline cellulose has a purity of 84.5 to 93.6% and a degree of polymerization of 156 to 402.
The invention has the beneficial effects that:
the high boiling point organic solvent is adopted to extract the straw cellulose, and because the high boiling point organic solvent has low volatility and good thermal stability and can be recovered by extraction, the pollution and the energy consumption are reduced. The spherical solid acid catalyst is adopted to catalyze partial hydrolysis of the straw cellulose to prepare the microcrystalline cellulose, the microcrystalline cellulose can be separated from a product through simple screening, the recovery is easy, the stability is high, and in the process of recycling for 4 times, the solid acid damage is small and the catalytic performance is basically kept unchanged. The microcrystalline cellulose obtained by the method has high purity and moderate polymerization degree, and is favorable for further fine raw material utilization. The preparation method disclosed by the invention is green and environment-friendly, and reduces environmental pollution and equipment corrosion.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the embodiment of the invention, the grain diameters of the wheat straw powder, the rice straw powder and the corn straw powder are all less than or equal to 40 meshes; the room temperature is 20-25 ℃; the drying temperature is 40 ℃, and the drying time is 10 hours; the temperature of cold distilled water used was 5 ℃.
Example 1
Adding wheat straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:2) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.05M) into a high-pressure reaction kettle, wherein the weight ratio of the wheat straw powder to the mixed solvent is 1:6, heating to 180 ℃, stirring for 4 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the wheat straw crude cellulose with the purity of 75.3 percent. Adding the wheat straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 4 wt% of sodium carbonate and 2 wt% of hydrogen peroxide, wherein the weight ratio of the wheat straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 8h at 70 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the wheat straw cellulose, wherein the cellulose content is 79.7%. Wheat straw cellulose and Amberlyst 45 are added into a flask in a weight ratio of 5:1, and then distilled water is added, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at 70 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the wheat straw microcrystalline cellulose with the purity of 84.6% and the polymerization degree of 372.
Example 2
Adding wheat straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the wheat straw powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the wheat straw crude cellulose with the purity of 79.7 percent. Adding the wheat straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 4 wt% of sodium carbonate and 2 wt% of hydrogen peroxide, wherein the weight ratio of the wheat straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 8h at 70 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the wheat straw cellulose, wherein the cellulose content is 86.7%. Wheat straw cellulose and Amberlyst 45 are added into a flask in a weight ratio of 5:1, and then distilled water is added, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at 70 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the wheat straw microcrystalline cellulose with purity of 89.8% and polymerization degree of 347.
Example 3
Adding wheat straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the wheat straw powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the wheat straw crude cellulose with the purity of 79.7 percent. Adding the wheat straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 6 wt% of sodium carbonate and 1 wt% of hydrogen peroxide, wherein the weight ratio of the wheat straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 7h at 60 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the wheat straw cellulose, wherein the cellulose content is 90.1%. Wheat straw cellulose and Amberlyst 45 are added into a flask in a weight ratio of 5:1, and then distilled water is added, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at 70 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the wheat straw microcrystalline cellulose with the purity of 92.2% and the polymerization degree of 337.
Example 4
Adding wheat straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the wheat straw powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the wheat straw crude cellulose with the purity of 79.7 percent. Adding the wheat straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 6 wt% of sodium carbonate and 1 wt% of hydrogen peroxide, wherein the weight ratio of the wheat straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 7h at 60 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the wheat straw cellulose, wherein the cellulose content is 90.1%. Wheat straw cellulose and Amberlyst 45 are added into a flask in a weight ratio of 2:1, and then distilled water is added, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at 70 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the wheat straw microcrystalline cellulose with the purity of 93.1 percent and the polymerization degree of 254.
Example 5
Adding wheat straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the wheat straw powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the wheat straw crude cellulose with the purity of 79.7 percent. Adding the wheat straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 6 wt% of sodium carbonate and 1 wt% of hydrogen peroxide, wherein the weight ratio of the wheat straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 7h at 60 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the wheat straw cellulose, wherein the cellulose content is 90.1%. Wheat straw cellulose and Amberlyst 45 are added into a flask in a weight ratio of 2:1, and then distilled water is added, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at the temperature of 80 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the wheat straw microcrystalline cellulose with the purity of 93.6 percent and the polymerization degree of 186.
Example 6
Adding wheat straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the wheat straw powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the wheat straw crude cellulose with the purity of 79.7 percent. Adding the wheat straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 6 wt% of sodium carbonate and 1 wt% of hydrogen peroxide, wherein the weight ratio of the wheat straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 7h at 60 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the wheat straw cellulose, wherein the cellulose content is 90.1%. Wheat straw cellulose and Amberlyst 45 are added into a flask in a weight ratio of 2:1, and then distilled water is added, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at 90 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the wheat straw microcrystalline cellulose with the purity of 93.4% and the polymerization degree of 197.
Example 7
Adding rice straw powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the rice straw powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6 hours, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the rice straw crude cellulose with the purity of 70.3 percent. Adding the rice straw crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 6 wt% of sodium carbonate and 1 wt% of hydrogen peroxide, wherein the weight ratio of the rice straw crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 7h at 60 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the rice straw cellulose, wherein the cellulose content is 84.6%. Adding rice straw cellulose and Amberlyst 45 into a flask in a weight ratio of 2:1, and then adding distilled water, wherein the weight of the distilled water is 10 times that of the cellulose. Stirring and reacting for 1h at 90 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the rice straw microcrystalline cellulose with the purity of 90.8% and the polymerization degree of 202.
Example 8
Adding corn stalk powder, a mixed solvent of N-methyl pyrrolidone and water (the volume ratio of the N-methyl pyrrolidone to the water is 1:1) and sulfuric acid (the concentration of the sulfuric acid in the solution is 0.03M) into a high-pressure reaction kettle, wherein the weight ratio of the corn stalk powder to the mixed solvent is 1:8, heating to 190 ℃, stirring for 6h, cooling to room temperature, centrifuging, and performing suction filtration to obtain a filtrate and a solid product. Washing the solid product with the same mixed solvent, combining the washing liquid and the filtrate, extracting the filtrate with chloroform, and recovering the organic solvent. The solid product is the corn straw crude cellulose with the purity of 75.9 percent. Adding the corn stalk crude cellulose into a round-bottom flask, and then adding the prepared mixed solution containing 6 wt% of sodium carbonate and 1 wt% of hydrogen peroxide, wherein the weight ratio of the corn stalk crude cellulose to the mixed solution is 1: 7.5. Heating and stirring for 7h at 60 ℃, cooling to room temperature, performing suction filtration, and drying to obtain the corn straw cellulose, wherein the cellulose content is 86.3%. Corn stalk cellulose and Amberlyst 45 were added to the flask in a weight ratio of 2:1, followed by distilled water, 10 times the weight of the cellulose. Stirring and reacting for 1h at 90 ℃, cooling to room temperature, adding cold distilled water with twice amount of the mixed solution, standing, filtering, washing the solid with distilled water to be neutral, drying, sieving, and separating the solid product from the catalyst to obtain the corn straw microcrystalline cellulose with the purity of 91.2% and the polymerization degree of 223.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (11)
1. A method for preparing microcrystalline cellulose by using crop straws is characterized by comprising the following steps:
(1) mixing straw powder, a mixed solvent and sulfuric acid, heating and stirring, and then cooling, centrifuging and filtering to obtain a filtrate and a solid product; the mixed solvent is a mixture of a high-boiling-point organic solvent and water;
(2) washing the solid product by using the mixed solvent same as the mixed solvent in the step (1), combining the filtrate with the mixed solvent, and extracting and recovering the high-boiling-point organic solvent to obtain the straw crude cellulose;
(3) mixing the straw crude cellulose with a weak base solution, heating and stirring, and then cooling, filtering and drying to obtain straw cellulose;
(4) mixing straw cellulose, a solid acid catalyst and water, heating, stirring, hydrolyzing, cooling, adding cold water at 4-6 ℃, standing, filtering, washing the obtained solid substance to be neutral, drying, sieving, separating and recovering the catalyst to obtain straw microcrystalline cellulose;
the solid acid catalyst is Amberlyst 15, Amberlyst 35, Amberlyst 36, Amberlyst 45, Amberlite IR120H, D001, D002, D072H or NKC-9.
2. The method of claim 1, wherein,
in the step (1), the weight ratio of the straw powder to the mixed solvent is 1: 4-12; the concentration of the sulfuric acid in the mixed solvent is 0.03-0.05M; in the mixed solvent, the volume ratio of the high-boiling-point organic solvent to water is 1-9: 1-4;
in the step (3), the weight ratio of the straw crude cellulose to the weak base solution is 1: 4-10;
in the step (4), the mass ratio of the solid acid catalyst to the straw cellulose is 1: 1-20.
3. The method of claim 1, wherein,
the straws are selected from at least one of wheat straws, rice straws, corn straws, sorghum straws and rape straws;
the straw powder is obtained by crushing straws, and the particle size of the straw powder is less than or equal to 40 meshes.
4. The method of claim 1, wherein,
the high boiling point organic solvent is at least one selected from N-methyl pyrrolidone, N-dimethylformamide, gamma-valerolactone, ethylene glycol, dimethylacetamide and dimethyl sulfoxide.
5. The method according to claim 1, wherein in the step (2), the high boiling point organic solvent is recovered by extraction with at least one extracting agent selected from chloroform, ethyl acetate and petroleum ether.
6. The method according to claim 1, wherein, in step (3),
the weak base solution is a mixture of hydrogen peroxide solution and sodium carbonate solution, or sodium carbonate solution.
7. The method according to claim 6, wherein, in step (3),
the weak base solution is a mixture of a hydrogen peroxide solution and a sodium carbonate solution, wherein the concentration of hydrogen peroxide in the mixture is 0.5-3 wt%, and the concentration of sodium carbonate in the mixture is 1-10 wt%.
8. The method according to claim 1, wherein, in step (4),
the solid acid catalyst is spherical particles, and the particle size is 300-1000 mu m.
9. The method of claim 1, wherein,
in the step (1), the heating and stirring temperature is 150-210 ℃, and the time is 2-10 h;
in the step (3), the heating and stirring temperature is 30-90 ℃, and the time is 1-20 h;
in the step (4), the hydrolysis temperature is 50-95 ℃, and the hydrolysis time is 0.5-6 h;
in the step (3) and the step (4), the drying temperature is 30-60 ℃ and the drying time is 8-12 hours.
10. Microcrystalline cellulose obtainable by the process of any one of claims 1 to 9.
11. The microcrystalline cellulose according to claim 10, wherein the microcrystalline cellulose has a purity of 84.5 to 93.6% and a degree of polymerization of 156 to 402.
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