CN113214196A - Method for preparing bio-based chemicals by using lignocellulose biomass as raw material - Google Patents
Method for preparing bio-based chemicals by using lignocellulose biomass as raw material Download PDFInfo
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- CN113214196A CN113214196A CN202110450652.5A CN202110450652A CN113214196A CN 113214196 A CN113214196 A CN 113214196A CN 202110450652 A CN202110450652 A CN 202110450652A CN 113214196 A CN113214196 A CN 113214196A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
Abstract
The invention discloses a method for preparing a bio-based chemical by using lignocellulose biomass as a raw material, which comprises the following steps: mixing a polar aprotic solvent with water according to a volume ratio of 10-50: 1 to obtain a composite solvent; adding a holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain a bio-based chemical; wherein the holocellulose raw material comprises cellulose and hemicellulose; the bio-based chemicals include one or more of furfural, 5-hydroxymethylfurfural, and levulinic acid. The method provided by the invention has the advantages that the holocellulose raw material can be directionally and directly hydrolyzed to generate the furfural compounds and/or levulinic acid, the steps are few, the process is simple, the comprehensive utilization process route of biomass resources is shortened, and the cost is reduced.
Description
Technical Field
The invention relates to the technical field of biomass recycling, in particular to a method for preparing a bio-based chemical by taking lignocellulose biomass as a raw material.
Background
With the development of industry and the increase of population, the energy consumption is continuously increased, and the problems of greenhouse effect, climate warming and the like caused by using petrochemical resources are increasingly serious, so that the continuous deterioration of the environment and the daily scarcity of energy are caused, the bottleneck for restricting the sustainable development of human society is formed, and the development of novel pollution-free energy with low price, safety, environmental protection and sustainable utilization is urgent. Lignocellulose is a renewable resource with abundant content and low price on the earth, the reserve is about 18000 million tons, which is equal to 640 million tons of petroleum, and the lignocellulose is a fossil resource substitute with great development prospect, and the high-value conversion and utilization of the lignocellulose are important research directions for biomass energy regeneration.
The lignocellulose mainly comprises hemicellulose, cellulose, lignin and other components, and the three components can be used for preparing high-added-value biomass chemicals. Cellulose and hemicellulose can be effectively converted into furfural compounds (furfural and 5-hydroxymethyl furfural), levulinic acid, fuel ethanol, saccharides and other substances. Among them, furfural compounds and levulinic acid are valuable intermediates and are listed as important platform compounds by the U.S. department of energy.
However, lignocellulose has a complex structure, and a large number of byproducts are generated in direct conversion, so that the selectivity of a target product is not high. Therefore, at present, the method for recycling biomass resources to obtain high-value bio-based chemicals generally includes the steps of pretreating lignocellulose and separating components to obtain a cellulose component and a hemicellulose component respectively, then establishing different reaction systems, catalyzing by using inorganic acid, and hydrolyzing by using the cellulose component and the hemicellulose component respectively to obtain bio-based chemicals such as furfural mixtures, levulinic acid and the like. However, the preparation method has long process route and high cost.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a bio-based chemical by using lignocellulose biomass as a raw material, and aims to solve the problem of long route of the existing preparation method.
In order to achieve the above object, the present invention provides a method for preparing a bio-based chemical from a lignocellulosic biomass, comprising the following steps:
mixing a polar aprotic solvent with water according to a volume ratio of 10-50: 1 to obtain a composite solvent;
adding a holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain a bio-based chemical;
wherein the holocellulose raw material comprises cellulose and hemicellulose;
the bio-based chemicals include one or more of furfural, 5-hydroxymethylfurfural, and levulinic acid.
Optionally, in the step of mixing a polar aprotic solvent with water according to a volume ratio of 10-50: 1 to obtain a composite solvent, the polar aprotic solvent includes at least one of acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, γ -valerolactone, N-dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran.
Alternatively, when the polar aprotic solvent is N, N-dimethylformamide, the bio-based chemical comprises levulinic acid; alternatively, the first and second electrodes may be,
when the polar aprotic solvent is one or more of gamma-valerolactone, acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, gamma-valerolactone, dimethyl sulfoxide and tetrahydrofuran, the bio-based chemical comprises furfural and/or 5-hydroxymethylfurfural; alternatively, the first and second electrodes may be,
when the polar aprotic solvent is a mixed solvent of N, N-dimethylformamide and other solvents, the bio-based chemicals comprise levulinic acid and at least one of furfural and 5-hydroxymethylfurfural, wherein the other solvents are one or more of gamma-valerolactone, acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, gamma-valerolactone, dimethyl sulfoxide and tetrahydrofuran.
Optionally, adding the holocellulose raw material and an organic acid catalyst into the composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemical, wherein the organic acid catalyst comprises at least one of sulfamic acid, sulfanilic acid, cobalt p-toluenesulfonate, nickel sulfamate, ammonium sulfamate and sodium sulfamate.
Optionally, in the step of adding an holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, separating and purifying to obtain the bio-based chemical, the holocellulose raw material comprises at least one of holocellulose and an holocellulose model compound, and the holocellulose model compound is a mixture of cellulose and hemicellulose.
Optionally, in the holocellulose model compound, the mass ratio of the cellulose to the hemicellulose is 1-4: 1.
Optionally, in the step of adding an holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemical, the weight ratio of the organic acid catalyst to the holocellulose raw material is 1: 2-10.
Optionally, adding the holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemical, wherein the hydrolysis reaction is performed at the temperature of 120-200 ℃ for 1-10 h.
Optionally, the holocellulose raw material and the organic acid catalyst are added into the composite solvent, and in the step of hydrolysis reaction, separation and purification to obtain the bio-based chemical, the hydrolysis reaction is carried out in a nitrogen atmosphere.
In the technical scheme provided by the invention, the holocellulose raw material is placed in a composite solvent formed by mixing a polar aprotic solvent and water according to a specific ratio, and is catalyzed by an organic acid catalyst, so that the holocellulose raw material can be directionally and directly hydrolyzed to generate furfural compounds and/or levulinic acid, the steps are few, the process is simple, the comprehensive utilization process route of biomass resources is shortened, and the cost is reduced; the hemicellulose and the cellulose are simultaneously converted, so that the method is simple and convenient, and the utilization efficiency of biomass resources is improved; compared with an inorganic acid catalyst, the adopted organic acid catalyst not only reduces the corrosion to equipment, but also promotes the directional conversion of the holocellulose raw material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing a bio-based chemical by using lignocellulose biomass as a raw material, and the method for preparing the bio-based chemical by using the lignocellulose biomass as the raw material provides a method which is short in process route, low in cost and capable of directionally and selectively obtaining a high-value bio-based chemical.
The method for preparing the bio-based chemicals by taking the lignocellulose biomass as the raw material comprises the following steps:
and step S10, mixing the polar aprotic solvent with water according to the volume ratio of 10-50: 1 to obtain the composite solvent.
In this embodiment, a polar aprotic solvent and water are mixed in a specific ratio to prepare a composite solvent, and the composite solvent is used in the subsequent hydrolysis step to facilitate the oriented progress of the hydrolysis reaction. Any polar aprotic solvent currently available on the market can be used in this step to obtain a composite solvent. In one embodiment, the polar aprotic solvent includes at least one of acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, γ -valerolactone, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran, that is, in this embodiment, the polar aprotic solvent may be any one of acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, γ -valerolactone, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran, or a mixture of any two thereof, or a mixture of any more (not less than two) thereof. When the polar aprotic solvent is a mixture of more than two solvents, the mixture is mixed with water according to a volume ratio of 10-50: 1 to obtain the composite solvent.
And step S20, adding the holocellulose raw material and the organic acid catalyst into the composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemical.
Wherein the material comprises cellulose and hemicellulose, that is to say, the biomass material for hydrolysis according to the invention is a material comprising cellulose and hemicellulose. Further, the material for the holocellulose may be a model compound of the holocellulose, or a mixture of the holocellulose and the holocellulose model compound. The comprehensive cellulose is also called total cellulose, is derived from agricultural wastes after lignin removal, and refers to a part (most of the parts are hemicellulose and cellulose and may contain a little lignin impurities which are difficult to remove) left by removing extracts and lignin from the agricultural wastes, and the agricultural wastes can be at least one of wheat straws, rice straws, corn straws, sorghum straws, rape straws, cotton stalks, bagasse, rice husks, corn cobs, bamboos, bamboo sawdust and wood chips; the holocellulose model compound is a direct mixture of cellulose and hemicellulose, and specifically, the mass ratio of the cellulose to the hemicellulose in the holocellulose model compound is 1-4: 1.
Wherein, the product obtained in the step comprises one or more of furfural, 5-hydroxymethyl furfural and levulinic acid. The hydrolysis direction can be controlled by controlling the type of the polar aprotic solvent in the composite solvent, so that the reaction can directionally generate levulinic acid, or coproduce furfural and 5-hydroxymethylfurfural, or simultaneously generate levulinic acid, furfural and 5-hydroxymethylfurfural, and during actual production, the method can be adjusted according to actual needs to obtain a target product. Specifically, in one embodiment, when the polar aprotic solvent is N, N-dimethylformamide, the reaction is directed to the production of levulinic acid, i.e. the bio-based chemical comprises levulinic acid; in another embodiment, when the polar aprotic solvent is one or more of gamma-valerolactone, acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, gamma-valerolactone, dimethyl sulfoxide, tetrahydrofuran, the reaction is directed to the production of furfural and/or 5-hydroxymethylfurfural, i.e., furfural-like compounds; in yet another embodiment, when the polar aprotic solvent is a mixed solvent of N, N-dimethylformamide and other solvents, and the other solvents are one or more of gamma-valerolactone, acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, gamma-valerolactone, dimethyl sulfoxide, tetrahydrofuran, the reaction produces a furfural-like compound and levulinic acid, wherein the furfural-like compound can be furfural, 5-hydroxymethylfurfural, or a mixture of furfural and 5-hydroxymethylfurfural.
In step S20, the acid catalyst is an organic acid or an organic acid metal salt, and specifically, in this embodiment, the organic acid catalyst includes at least one of sulfamic acid, sulfanilic acid, cobalt sulfamate p-toluenesulfonate, nickel sulfamate, ammonium sulfamate, and sodium sulfamate. By adopting the organic acid and the metal salt thereof as the catalyst, the hemicellulose and the cellulose can be converted simultaneously, and the conversion direction can be controlled.
In order to ensure that the hemicellulose and the cellulose can be converted simultaneously, the weight ratio of the organic acid catalyst to the holocellulose raw material is 1: 1-10.
In addition, in order to hydrolyze cellulose and hemicellulose smoothly, the hydrolysis reaction is carried out at the temperature of 120-200 ℃ for 1-10 h.
In addition, the hydrolysis reaction is carried out in a nitrogen atmosphere, and compared with the current method of adopting a large amount of organic solvents and inorganic liquid acid catalysts, the reaction in the nitrogen atmosphere can reduce the generation of byproducts and avoid environmental pollution.
In the technical scheme provided by the invention, the holocellulose raw material is placed in a composite solvent formed by mixing a polar aprotic solvent and water according to a specific ratio, and is catalyzed by an organic acid catalyst, so that the holocellulose raw material can be directionally and directly hydrolyzed to generate furfural compounds and/or levulinic acid, the steps are few, the process is simple, the comprehensive utilization process route of biomass resources is shortened, and the cost is reduced; the hemicellulose and the cellulose are simultaneously converted, so that the method is simple and convenient, and the utilization efficiency of biomass resources is improved; compared with an inorganic acid catalyst, the adopted organic acid catalyst not only reduces the corrosion to equipment, but also promotes the directional conversion of the holocellulose raw material.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
Adding 4g of sulfanilic acid, 50mL of gamma-valerolactone/water mixed solution (19:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 1MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 5 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 28.5%, the yield of 5-hydroxymethylfurfural is 15.0%, and levulinic acid is hardly detected.
Example 2
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (19:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 42.4%, the yield of 5-hydroxymethylfurfural is 35.8%, and levulinic acid is hardly detected.
Example 3
Adding 4g of cobalt sulfamate, 50mL of gamma-valerolactone/water mixed solution (19:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 17.7%, the yield of 5-hydroxymethylfurfural is 3.5%, and levulinic acid is hardly detected.
Example 4
Adding 3g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (19:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 34.1%, the yield of 5-hydroxymethylfurfural is 30.5%, and levulinic acid is hardly detected.
Example 5
Adding 1g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (19:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 24.1%, the yield of 5-hydroxymethylfurfural is 20.5%, and levulinic acid is hardly detected.
Example 6
Adding 5g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (39:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 44.2%, the yield of 5-hydroxymethylfurfural is 34.8%, and levulinic acid is hardly detected.
Example 7
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (39:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 21.2%, the yield of 5-hydroxymethylfurfural is 24.7%, and levulinic acid is hardly detected.
Example 8
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 63.8%, the yield of 5-hydroxymethylfurfural is 35.9%, and levulinic acid is hardly detected.
Example 9
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 170 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 34.5%, the yield of 5-hydroxymethylfurfural is 28.8%, and levulinic acid is hardly detected.
Example 10
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 190 ℃ for 4h, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 23.7%, the yield of 5-hydroxymethylfurfural is 22.4%, and levulinic acid is hardly detected.
Example 11
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 1h, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 37.1%, the yield of 5-hydroxymethylfurfural is 33.6%, and levulinic acid is hardly detected.
Example 12
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 6h, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 36.8%, the yield of 5-hydroxymethylfurfural is 32.8%, and levulinic acid is hardly detected.
Example 13
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 5g of cellulose and 5g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 65.7%, the yield of 5-hydroxymethylfurfural is 38.1%, and levulinic acid is hardly detected.
Example 14
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of corncob holocellulose into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, quickly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and carrying out reduced pressure distillation to obtain a product, wherein the yield of furfural is 34.9%, the yield of 5-hydroxymethylfurfural is 29.8%, and levulinic acid is hardly detected.
Example 15
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of wheat straw holocellulose into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, quickly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and carrying out reduced pressure distillation to obtain a product, wherein the yield of furfural is 27.3%, the yield of 5-hydroxymethylfurfural is 29.7%, and levulinic acid is hardly detected.
Example 16
Adding 4g of sulfamic acid, 50mL of a composite solvent (a polar aprotic solvent/water mixed solution, 25:1, v: v, wherein the polar aprotic solvent is a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, and the dimethyl sulfoxide is N, N-dimethylformamide which is 1:2, v: v: v: v) and 10g of a holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4h, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of the levulinic acid is 32.3%, the yield of the 5-hydroxymethylfurfural is 0.6%, and the yield of the furfural is 3.7%.
Example 17
Adding 4g of sulfamic acid, 50mL of N, N-dimethylformamide/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of levulinic acid is 48.5%, and 5-hydroxymethylfurfural and furfural are hardly detected.
Example 18
Adding a mixture of 4g of nickel sulfamate and sodium sulfamate, 50mL of N, N-dimethylformamide/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, quickly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of levulinic acid is 18.9%, and 5-hydroxymethylfurfural and furfural are hardly detected.
Example 19
Adding 4g of p-toluenesulfonic acid, a mixture of sodium sulfamate and sulfamic acid, 50mL of N, N-dimethylformamide/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa nitrogen for three times, filling 3MPa nitrogen, heating and stirring at 180 ℃ for 4 hours, quickly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of levulinic acid is 33.8%, and 5-hydroxymethylfurfural and furfural are hardly detected.
Example 20
Adding 4g of sulfamic acid, 50mL of a composite solvent (a polar aprotic solvent/water mixed solution, 25:1, v: v, wherein the polar aprotic solvent is a mixed solvent of 2-methyltetrahydrofuran and gamma-valerolactone, the 2-methyltetrahydrofuran is tetrahydrofuran which is 1:2, v: v: v) and 10g of a holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4h, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of 5-hydroxymethylfurfural is 31.7%, the yield of furfural is 21.6%, and levulinic acid is hardly detected.
Example 21
Adding 4g of sulfamic acid, 50mL of a composite solvent (a polar aprotic solvent/water mixed solution, 25:1, v: v, wherein the polar aprotic solvent is a mixed solvent of methyl isobutyl ketone and gamma-valerolactone, and the methyl isobutyl ketone is gamma-valerolactone which is 1:2, v: v) and 10g of a holocellulose model compound (containing 8g of cellulose and 2g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of 5-hydroxymethylfurfural is 18.9%, the yield of furfural is 28.7%, and levulinic acid is hardly detected.
Example 22
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (10:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 37.6%, the yield of 5-hydroxymethylfurfural is 25.1%, and levulinic acid is hardly detected.
Example 23
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (50:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 21.2%, the yield of 5-hydroxymethylfurfural is 18.4%, and levulinic acid is hardly detected.
Example 24
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 6g of cellulose and 4g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 180 ℃ for 10 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 67.4%, the yield of 5-hydroxymethylfurfural is 32.4%, and levulinic acid is hardly detected.
Example 25
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 5g of cellulose and 5g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 200 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of 5-hydroxymethylfurfural is 30.2%, the yield of furfural is 50.8%, and levulinic acid is hardly detected.
Example 26
Adding 4g of sulfamic acid, 50mL of gamma-valerolactone/water mixed solution (25:1, v: v) and 10g of holocellulose model compound (containing 5g of cellulose and 5g of xylan) into a 500mL high-pressure reaction kettle, replacing air in the reaction kettle with 3MPa of nitrogen for three times, then filling 3MPa of nitrogen, heating and stirring at 120 ℃ for 4 hours, rapidly cooling to room temperature, slowly releasing pressure, filtering, collecting filtrate, and distilling under reduced pressure to obtain a product, wherein the yield of furfural is 35.7%, and 5-hydroxymethylfurfural and levulinic acid are hardly detected.
Comparative example 1
The procedure was the same as in example 1 except that sulfanilic acid in example 1 was replaced with sulfuric acid. The furfural yield in the product was found to be 19.6%, and 5-hydroxymethylfurfural and levulinic acid were hardly detected.
Comparative example 2
The procedure was the same as in example 1 except that gamma-valerolactone in example 1 was changed to ethanol. The furfural yield in the product was 3.6%, and almost no 5-hydroxymethylfurfural yield and levulinic acid were detected.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (9)
1. A method for preparing a bio-based chemical by using lignocellulose biomass as a raw material is characterized by comprising the following steps:
mixing a polar aprotic solvent with water according to a volume ratio of 10-50: 1 to obtain a composite solvent;
adding a holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain a bio-based chemical;
wherein the holocellulose raw material comprises cellulose and hemicellulose;
the bio-based chemicals include one or more of furfural, 5-hydroxymethylfurfural, and levulinic acid.
2. The method for preparing a bio-based chemical from a lignocellulosic biomass as claimed in claim 1, wherein the step of mixing a polar aprotic solvent with water in a volume ratio of 10 to 50:1 to obtain the composite solvent, the polar aprotic solvent comprises at least one of acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, γ -valerolactone, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.
3. The method of claim 2, wherein when the polar aprotic solvent is N, N-dimethylformamide, the bio-based chemical comprises levulinic acid; alternatively, the first and second electrodes may be,
when the polar aprotic solvent is one or more of gamma-valerolactone, acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, gamma-valerolactone, dimethyl sulfoxide and tetrahydrofuran, the bio-based chemical comprises furfural and/or 5-hydroxymethylfurfural; alternatively, the first and second electrodes may be,
when the polar aprotic solvent is a mixed solvent of N, N-dimethylformamide and other solvents, the bio-based chemicals comprise levulinic acid and at least one of furfural and 5-hydroxymethylfurfural, wherein the other solvents are one or more of gamma-valerolactone, acetonitrile, methyl isobutyl ketone, 2-methyltetrahydrofuran, gamma-valerolactone, dimethyl sulfoxide and tetrahydrofuran.
4. The method for preparing bio-based chemicals from lignocellulosic biomass as claimed in claim 1, wherein the step of adding the holocellulose raw material and an organic acid catalyst to the composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemicals, wherein the organic acid catalyst comprises at least one of sulfamic acid, sulfanilic acid, cobalt p-toluenesulfonate, nickel sulfamate, ammonium sulfamate, and sodium sulfamate.
5. The method for preparing bio-based chemicals from lignocellulosic biomass as claimed in claim 1, wherein the step of adding an holocellulose raw material and an organic acid catalyst into a composite solvent, performing hydrolysis reaction, separating and purifying to obtain bio-based chemicals, the holocellulose raw material comprises at least one of holocellulose and an holocellulose model compound, and the holocellulose model compound is a mixture of cellulose and hemicellulose.
6. The method for preparing a bio-based chemical from a lignocellulosic biomass as claimed in claim 5, wherein the mass ratio of the cellulose to the hemicellulose in the holocellulose model compound is 1 to 4: 1.
7. The method for preparing a bio-based chemical from a lignocellulosic biomass as claimed in claim 1, wherein the weight ratio of the organic acid catalyst to the holocellulose raw material is 1: 2-10 in the step of adding the holocellulose raw material and the organic acid catalyst to a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemical.
8. The method for preparing a bio-based chemical from a lignocellulosic biomass as claimed in claim 1, wherein the step of adding the holocellulose raw material and the organic acid catalyst into a composite solvent, performing hydrolysis reaction, and separating and purifying to obtain the bio-based chemical, wherein the hydrolysis reaction is performed at a temperature of 120 to 200 ℃ for 1 to 10 hours.
9. The method for preparing bio-based chemicals from lignocellulosic biomass as claimed in claim 1, wherein the step of adding the holocellulose raw material and the organic acid catalyst to the composite solvent, performing hydrolysis reaction, separating and purifying to obtain the bio-based chemicals, wherein the hydrolysis reaction is performed under nitrogen atmosphere.
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| CN115717007A (en) * | 2022-05-13 | 2023-02-28 | 北京林业大学 | Method for separating and extracting pseudolignin from biomass |
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| CN114478225A (en) * | 2022-02-16 | 2022-05-13 | 四川大学 | Method for preparing levulinic acid by synergistically promoting cellulose conversion through alkylammonium halide and sodium halide |
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