CN108940313B - Biomass carbon-based solid acid catalyst and preparation method and application thereof - Google Patents
Biomass carbon-based solid acid catalyst and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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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
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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
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Abstract
The invention provides a preparation method and application of a biomass carbon-based solid acid catalyst, which comprises the following steps: A) soaking biomass containing nitrogen compounds in an acid solution, and filtering to obtain a solid product; B) carbonizing the solid product to obtain a porous carbon carrier; C) and reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst. The invention impregnates and carbonizes the biomass containing nitrogen compound to obtain the porous carbon carrier; the diversified surface chemical components of the carbonized product have better sulfonic acid group loading property compared with a highly carbonized surface, so that the Bronsted acid loading capacity of the carbonized product is improved, and the conversion efficiency of various sugars is promoted. The adjustable carbon-based carrier porous structure formed by the invention enables sulfonic acid groups to be firmly loaded in the pore channels, and the pore channels after being loaded are mesoporous and macroporous, thereby being beneficial to the contact of a substrate and an acid site and keeping better recycling property. The biomass carbon-based solid acid catalyst disclosed by the invention is high in catalytic activity, good in stability and high in catalytic conversion efficiency.
Description
Technical Field
The invention relates to the technical field of biomass chemical utilization, in particular to a biomass carbon-based solid acid catalyst and a preparation method and application thereof.
Background
With the increasing environmental pollution and energy shortage caused by the use of traditional fossil energy, the preparation of chemicals and liquid fuels from renewable biomass raw materials has received great attention. 5-Hydroxymethylfurfural (HMF) is an important biomass-based platform compound, and can be converted into various chemicals such as levulinic acid, 2, 5-dimethylfuran, 2, 5-furandicarboxylic acid, 2, 5-furandimethanol, 1, 6-hexanediol, maleic anhydride and the like which can be used for medicines, fuels, plastic products and fine chemicals through various chemical reactions.
The 5-hydroxymethylfurfural is mainly obtained by catalytic dehydration and conversion of carbohydrate acid, wherein the carbohydrate can be six-carbon monosaccharide, can also be glycan or even direct biomass raw material, and fructose and glucose are the most widely studied reactants. The acid catalysts used for the preparation of HMF by the catalytic conversion of hexoses are mainly divided into homogeneous catalysts and solid catalysts. The homogeneous catalyst usually comprises inorganic acids (hydrochloric acid, sulfuric acid and nitric acid), organic acids (formic acid, acetic acid and citric acid) and metal chlorides (aluminum chloride, chromium chloride and copper chloride), but the adoption of the homogeneous catalyst has unsustainability due to the problems of equipment corrosion, difficult recovery, environmental pollution and the like.
Solid catalysts are receiving more attention from researchers due to higher reactivity, recyclability and environmental friendliness, and currently used solid catalysts include resins, carbon-based solid acids, zeolites, metal oxides and the like, and achieve better effects. However, many solid catalysts have problems of unstable activity, unstable structure, low cyclicity and low efficiency. In addition, in order to increase the yield, expensive or toxic substances such as ionic liquids and dimethyl sulfoxide are often used as solvents, and industrial applicability is poor. In addition, for the conversion of glucose to HMF, it requires a stronger broenstronic acid: (
acid) and Lewis acids (Lewis acids), whereas conventional solid acids often contain only a single type of acidic site.
The existing biomass carbon-based solid acid catalyst has a general recycling effect, and usually has a good initial effect in the catalytic preparation process of HMF, and generally only contains the Bronsted acid, so that the yield of the HMF converted from glucose is too low. Therefore, an efficient and stable solid acid and an environment-friendly catalytic method are sought, and the method plays a key role in promoting the industrial preparation of the HMF.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a biomass carbon-based solid acid catalyst, which has high catalytic activity, good stability and high catalytic conversion efficiency.
The invention provides a preparation method of a biomass carbon-based solid acid catalyst, which comprises the following steps:
A) soaking biomass containing nitrogen compounds in an acid solution, and filtering to obtain a solid product;
B) carbonizing the solid product to obtain a porous carbon carrier;
C) and reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst.
Preferably, the biomass containing the nitrogen compounds in the step A) is tobacco stems, eggplant straws or bean straws; the acid solution is a phosphoric acid or pyrophosphoric acid solution with the mass concentration of 10-50%.
Preferably, the dipping time in the step A) is 1-24 h; the mass ratio of the biomass containing the nitrogen compounds to the acid solution is as follows: 1: (0.4-2); the mass ratio of the sulfanilic acid to the isoamyl nitrite is 1: 3-3: 1.
preferably, the reaction in step B) is carried out under the protection of inert gas; the carbonization temperature is 300-700 ℃; the carbonization time is 1-10 h.
Preferably, the reaction temperature in the step C) is 60-100 ℃; the reaction time is 4-24 h.
The invention provides a biomass carbon-based solid acid catalyst which is prepared by any one of the preparation methods in the technical scheme.
The invention provides a preparation method of 5-hydroxymethylfurfural, which comprises the following steps:
mixing glucose or fructose, a solvent and the catalyst prepared by the preparation method of any one of the technical schemes, stirring and reacting to obtain the 5-hydroxymethylfurfural.
Preferably, the reaction temperature is 80-250 ℃, and the catalytic dehydration time is 1-600 min.
The invention provides a preparation method of furfural, which comprises the following steps:
mixing xylose, a solvent and the catalyst prepared by the preparation method of any one of claims 1-5, stirring and reacting to obtain furfural.
The invention provides application of the catalyst prepared by the preparation method in any one of the technical schemes in preparation of 5-hydroxymethylfurfural or furfural.
Compared with the prior art, the invention provides a preparation method of a biomass carbon-based solid acid catalyst, which comprises the following steps: A) soaking biomass containing nitrogen compounds in an acid solution, and filtering to obtain a solid product; B) carbonizing the solid product to obtain a porous carbon carrier; C) and reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst. The invention impregnates and carbonizes the biomass containing nitrogen compound to obtain the porous carbon carrier; the diversified surface chemical components of the carbonized surface have better sulfonic acid group loading property than the surface with high carbonization degree, and the Bronsted acid (A), (B) and (C) are improved
acid) loading capacity, and promoting the conversion efficiency of various sugars; then, the catalyst is prepared by hydrolyzing the isoamyl nitrite and sulfonating the sulfanilic acid. The adjustable carbon-based carrier porous structure formed by the invention enables sulfonic acid groups to be firmly loaded in the pore channels and the surface, and the pore channels after being loaded are all in mesoporous and macroporous structures, thereby being beneficial to the contact of a substrate and an acid site and simultaneously keeping better recycling property. The biomass carbon-based solid acid catalyst disclosed by the invention is high in catalytic activity, good in stability and high in catalytic conversion efficiency.
Detailed Description
The invention provides a biomass carbon-based solid acid catalyst, and a preparation method and application thereof, and a person skilled in the art can realize the catalyst by appropriately improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a preparation method of a biomass carbon-based solid acid catalyst, which comprises the following steps:
A) soaking biomass containing nitrogen compounds in an acid solution, and filtering to obtain a solid product;
B) carbonizing the solid product to obtain a porous carbon carrier;
C) and reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst.
The invention first impregnates the biomass containing nitrogen compounds in an acid solution.
Biomass containing nitrogen compounds of the present invention includes, but is not limited to, tobacco stems or soybean stalks; the embodiment of the invention adopts tobacco stems.
In the invention, preferably, the biomass containing the nitrogen compound is dried and ground at 100-105 ℃. The invention is not limited to the specific manner of said grinding, as is well known to those skilled in the art; the mesh size of the grinding is not limited in the present invention, and may be preferably 40 to 60 mesh.
The biomass containing nitrogen compounds after being ground is soaked in acid solution.
According to the invention, the acid solution is preferably a phosphoric acid or pyrophosphoric acid solution with a mass concentration of 10% to 50%; more preferably a phosphoric acid or pyrophosphoric acid solution having a mass concentration of 15% to 48%. The soaking time is preferably 1-24 h; more preferably 5-20 h; most preferably 6-15 h.
Wherein the mass ratio of the biomass containing the nitrogen compounds to the acid solution is preferably 1: (0.4-2); more preferably 1: (0.8-1.8); most preferably 1: (1-1.6).
The present invention is not limited to the specific manner of impregnation, and those skilled in the art will be familiar with the present invention.
After impregnation, filtration is carried out to obtain filtrate and a solid product.
And carbonizing the solid product to obtain the porous carbon carrier.
The carbonization is preferably carried out under the protection of inert gas; the inert gas may be nitrogen, helium, or the like.
The carbonization is preferably performed for 1-10 h at the temperature of 300-700 ℃; more preferably charring for 1-8 h under the condition of 300-600 ℃; most preferably, the carbonization time is 1 to 6 hours under the condition of 300 to 500 ℃.
And (3) obtaining a black solid after carbonization, and washing the black solid by using water until the pH value is neutral, wherein the frequency and the mode of the washing are not limited in the invention and can be known by a person skilled in the art.
The porous carbon carrier is obtained by drying and removing water after washing.
And reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst.
The preparation method comprises the steps of firstly soaking porous carbon in water, stirring, and then sequentially adding sulfanilic acid and isoamyl nitrite.
The present invention is not limited to the specific manner of stirring, and those skilled in the art will be familiar with the present invention.
The mass ratio of sulfanilic acid to isoamyl nitrite is preferably 1: 3-3: 1; more preferably 1: 0.5 to 1. The mass ratio of the porous carbon carrier to the sulfanilic acid to the isoprene nitrite is preferably 1: 1-6: 0.5 to 3; most preferably 1:4: 2.
After stirring, heating and refluxing for reaction for 4-24 h at 60-100 ℃; more preferably, the heating reflux reaction is carried out for 10-20 h at the temperature of 80-90 ℃; most preferably, the reaction is performed for 12 to 18 hours at a temperature of 80 to 85 ℃ by heating and refluxing. And after the reaction is finished, carrying out solid-liquid separation and washing, and drying for 2-24 hours at the temperature of 60-120 ℃ in vacuum to obtain the catalyst. More preferably, the catalyst is obtained by drying for 12-20 hours under the condition of vacuum 80-100 ℃.
The invention provides a biomass carbon-based solid acid catalyst which is prepared by any one of the preparation methods in the technical scheme.
The invention provides a preparation method of a biomass carbon-based solid acid catalyst, which comprises the following steps: A) soaking biomass containing nitrogen compounds in an acid solution, and filtering to obtain a solid product; B) carbonizing the solid product to obtain a porous carbon carrier; C) and reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst. The invention will contain nitrogenThe biomass of the compound is impregnated and carbonized to obtain a porous carbon carrier; the diversified surface chemical components of the carbonized surface have better sulfonic acid group loading property than the surface with high carbonization degree, and the Bronsted acid (A), (B) and (C) are improved
acid) loading capacity, and promoting the conversion efficiency of various sugars; then, the catalyst is prepared by hydrolyzing the isoamyl nitrite and sulfonating the sulfanilic acid. The adjustable carbon-based carrier porous structure formed by the invention enables sulfonic acid groups to be firmly loaded in the pore channels and the surface, and the pore channels after being loaded are all in mesoporous and macroporous structures, thereby being beneficial to the contact of a substrate and an acid site and simultaneously keeping better recycling property. The biomass carbon-based solid acid catalyst disclosed by the invention is high in catalytic activity, good in stability and high in catalytic conversion efficiency.
The invention provides a preparation method of 5-hydroxymethylfurfural, which comprises the following steps:
mixing glucose or fructose, a solvent and the catalyst prepared by the preparation method of any one of the technical schemes, stirring and reacting to obtain the 5-hydroxymethylfurfural.
In the invention, glucose or fructose, a solvent and the catalyst prepared by the preparation method of any one of the technical schemes are preferably mixed and stirred in a pressure-resistant reaction vessel for reaction.
The solvent of the present invention includes, but is not limited to, pure organic solvents such as gamma-valerolactone (GVL), gamma-butyrolactone (GBL), etc., or mixed solvents thereof with water. The present invention is not limited in its source, and may be commercially available.
The invention adopts nontoxic green solvent which can be obtained by biomass conversion, and is beneficial to environmental protection and circular economy.
The mass ratio of the sugar (glucose or fructose) to the solvent is preferably 0.01-0.05), the mass ratio of the sugar (glucose or fructose) to the catalyst is preferably 20-1, more preferably 2-5, and the mass ratio of the organic solvent to water in the mixed solvent is preferably 1-200: 1; more preferably 5-100: 1; most preferably 10-50: 1.
The mixed solvent of the invention can also be a pure organic solvent without adding water.
The reaction temperature is preferably 80-250 ℃, more preferably 100-200 ℃, most preferably 120-180 ℃, and the catalytic dehydration time is preferably 1-600 min; more preferably 10-300 min; most preferably 20-60 min.
The reaction is preferably a stirring reaction, and the stirring rotating speed is preferably 300-600 r/min; more preferably 400 to 500 r/min.
And filtering the reaction solution after the reaction is finished to obtain the 5-hydroxymethylfurfural.
The invention provides a preparation method of furfural, which comprises the following steps:
mixing xylose, a solvent and the catalyst prepared by the preparation method of any one of claims 1-5, stirring and reacting to obtain furfural.
In the invention, xylose, a solvent and the catalyst prepared by the preparation method of any one of the technical schemes are preferably mixed and stirred in a pressure-resistant reaction vessel for reaction.
The solvent of the present invention includes but is not limited to gamma-valerolactone, gamma-butyrolactone (GBL) and other pure organic solvents or their mixed solvents with water. The present invention is not limited in its source, and may be commercially available.
The mass ratio of the sugar (glucose or fructose) to the solvent in the invention can be preferably 0.01-0.05), the mass ratio of the sugar (glucose or fructose) to the catalyst in the invention is preferably 20-1, and most preferably 2-5), and the mass ratio of the organic solvent to water in the mixed solvent in the invention is preferably 1-200: 1; more preferably 5-100: 1; most preferably 10-50: 1. The mixed solvent of the invention can also be a pure organic solvent without adding water.
The reaction temperature (of sugar conversion) is preferably 80-250 ℃, more preferably 100-200 ℃, most preferably 120-180 ℃, and the catalytic dehydration time is preferably 1-600 min; more preferably 10-300 min; most preferably 20-60 min.
The reaction is preferably a stirring reaction, and the stirring rotating speed is preferably 300-600 r/min; more preferably 400 to 500 r/min.
And filtering the reaction solution after the reaction is finished to obtain the furfural.
The invention provides application of the catalyst prepared by the preparation method in any one of the technical schemes in preparation of 5-hydroxymethylfurfural or furfural.
The catalyst prepared by the invention is prepared from the original biomass, so that waste is turned into wealth, the economy is good, the original biomass rich in nitrogen-containing compounds is used as the raw material, the surface of the prepared carbon-based carrier has rich hydroxyl, carboxyl and various nitrogen-containing functional groups, and the catalyst has good catalytic synergistic promotion effect on the preparation of HMF (high molecular weight polyethylene) from sugar through acid catalytic dehydration.
The diversified surface chemical components of the carbonized solid product have better sulfonic acid group loading property than the highly carbonized surface, and the Bronsted acid (A) and (B) are improved
acid) loading capacity, and promoting the conversion efficiency of various sugars; the raw biomass of the invention is rich in some mineral metals, and can form Lewis acid (Lewis acid) sites after carbonization without additional load, thus having good effect on the catalytic conversion of glucose; the adjustable carbon-based carrier porous structure formed by the invention enables sulfonic acid groups to be firmly loaded in the pore channels and the surface, and the pore channels after being loaded are all in mesoporous and macroporous structures, thereby being beneficial to the contact of a substrate and an acid site and simultaneously keeping better recycling property. The method has the advantages that the catalytic reaction is rapid, the yield of converting fructose into HMF can reach 93.7% and the yield of converting glucose into HMF can reach 43.8% within 10-30 min.
The invention adopts a nontoxic green solvent which can be converted by biomass or a mixed solvent of the nontoxic green solvent and water, and has green process and high yield. By combining the characteristics, the waste biomass is changed into valuable, the prepared carbon-based solid acid catalyst can efficiently catalyze saccharides to obtain HMF, the yield of a target product is high, the catalyst has good recycling property, and a reaction system is green and environment-friendly and has very good industrial application value.
In order to further illustrate the present invention, the following describes a biomass carbon-based solid acid catalyst, a preparation method and applications thereof in detail with reference to examples.
Examples 1-4 preparation of catalysts A-D
Taking 10g of ground tobacco stem powder as a raw biomass raw material rich in nitrogen-containing compounds, soaking the raw biomass raw material in 45% pyrophosphoric acid solution for 12h, wherein the mass ratio of pyrophosphoric acid to tobacco stems is 1.3:1, and then filtering the filtrate; carbonizing the obtained solid for 1h at 350,400,450,500 ℃ under the protection of inert gas to obtain black solids with serial numbers of 1-4, washing the black solids with deionized water until the pH value is neutral, and drying to remove moisture to obtain the porous carbon carrier with serial numbers of 1-4. In the sulfonation process, a certain amount of porous carbon is soaked in water and stirred, then p-aminobenzene sulfonic acid and isoamyl nitrite (mass: 2: 1) are sequentially added to reflux at 80 ℃ for 12 hours, after that, solid-liquid separation and washing are carried out, and drying is carried out at 80 ℃ for 12 hours in vacuum to obtain corresponding catalyst numbers A-D in sequence.
Examples 5 to 8
Adding 0.1g of fructose, 4.7ml of gamma-valerolactone, 0.3ml of water and 0.05g of catalyst into a 15ml pressure-resistant tube, reacting at the temperature of 130 ℃ for 30min at the rotating speed of 500r/min, filtering the reaction solution after the reaction is finished, and detecting the sugar and HMF products by using HPLC. The specific results are shown in Table 1.
TABLE 1 conversion of fructose, HMF yield and selectivity under different catalysis
| Catalyst and process for preparing same | Conversion (%) | Yield (%) | Selectivity (%) |
| A | 99.95 | 93.69 | 93.73 |
| B | 99.42 | 91.26 | 91.79 |
| C | 99.27 | 90.28 | 90.95 |
| D | 99.06 | 89.70 | 90.55 |
Examples 9 to 12
Adding 0.1g of glucose, 4.7ml of gamma-valerolactone, 0.3ml of water and 0.05g of catalyst into a 15ml pressure resistant tube, reacting at the temperature of 180 ℃ for 30min at the rotating speed of 500r/min, filtering reaction liquid after the reaction is finished, and detecting sugar and HMF products by using HPLC. The specific results are shown in Table 2.
TABLE 2 conversion of glucose, yield of HMF and selectivity under different catalysis
Examples 13 to 16
Adding 0.1g of xylose, 5.0ml of gamma-valerolactone and 0.05g of catalyst into a 15ml pressure resistant tube, reacting at the temperature of 170 ℃ for 30min at the rotating speed of 500r/min, filtering reaction liquid after the reaction is finished, and detecting sugar and HMF products by using HPLC. The specific results are shown in Table 3.
TABLE 3 yield and selectivity of xylose conversion furfural under different catalysis
| Catalyst and process for preparing same | Conversion (%) | Yield (%) | Selectivity (%) |
| A | 98.95 | 83.52 | 84.41 |
| B | 98.28 | 82.32 | 83.77 |
| C | 97.67 | 79.64 | 81.54 |
| D | 97.18 | 77.27 | 79.52 |
Examples 17 to 20
Adding 0.1g of fructose or glucose and 0.05g of catalyst A into a 15ml pressure resistant tube, using 5ml of pure GVL, 4.55ml of GVL and 0.45ml of water mixed solvent respectively as the solvent, reacting at the rotation speed of 500r/min for 30min at the temperature of 130 ℃ of fructose and at the temperature of 180 ℃ of glucose for 30min, filtering the reaction solution after the reaction is finished, and detecting the products of the fructose and the HMF by using HPLC. The specific results are shown in Table 4.
TABLE 4 conversion of sugars, yield of HMF and selectivity for different reaction solvents
Examples 21 to 24
Adding 0.1g of fructose or glucose, 4.7ml of gamma-valerolactone and 0.3ml of water into a 15ml pressure-resistant tube, wherein the using amounts of the catalyst A are 0.06g and 0.03g respectively, reacting at the rotation speed of 500r/min for 30min at the temperature of 130 ℃ of fructose and at the temperature of 180 ℃ of glucose for 30min, filtering the reaction solution after the reaction is finished, and detecting the products of sugar and HMF by using HPLC. The specific results are shown in Table 5.
TABLE 5 conversion of sugars, HMF yield and selectivity for different catalyst dosages
| Amount of catalyst (g) | Candy | Conversion (%) | Yield (%) | Selectivity (%) |
| 0.06 | Fructose | 99.96 | 91.62 | 91.66 |
| 0.03 | Fructose | 98.63 | 87.87 | 89.09 |
| 0.06 | Glucose | 96.79 | 43.05 | 44.48 |
| 0.03 | Glucose | 89.41 | 38.55 | 43.11 |
Examples 25 to 29
Adding 0.1g of fructose, 4.7ml of gamma-valerolactone, 0.3ml of water and 0.05g of catalyst into a 15ml pressure-resistant tube, reacting at the temperature of 130 ℃ for 30min at the rotating speed of 500r/min, filtering the reaction solution after the reaction is finished, and detecting the sugar and HMF products by using HPLC. After filtration of the solid product, it was washed repeatedly with ethanol and then dried at 110 ℃ for 2h and used directly in the reaction. The specific results are shown in Table 6.
TABLE 6 conversion of fructose, HMF yield and selectivity with catalyst recycle
| Number of cycles | Conversion (%) | Yield (%) | Selectivity (%) |
| 1 | 99.95 | 93.69 | 93.73 |
| 2 | 99.83 | 92.82 | 92.98 |
| 3 | 99.22 | 90.33 | 91.04 |
| 4 | 98.87 | 89.47 | 90.49 |
| 5 | 98.13 | 86.62 | 88.27 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a biomass carbon-based solid acid catalyst comprises the following steps:
A) drying and grinding biomass containing nitrogen compounds at 100-105 ℃, soaking in an acid solution, and filtering to obtain a solid product; the biomass containing the nitrogen compounds is tobacco stems, eggplant straws or bean straws; the ground mesh number is 40-60 meshes;
B) carbonizing the solid product to obtain a porous carbon carrier; the reaction is carried out under the protection of inert gas; the carbonization temperature is 300-700 ℃; the carbonization time is 1-10 h;
C) and reacting the porous carbon carrier with sulfanilic acid and isoamyl nitrite, and sulfonating to obtain the catalyst.
2. The method according to claim 1, wherein the acid solution in step a) is a phosphoric acid or pyrophosphoric acid solution having a concentration of 10 to 50% by mass.
3. The preparation method according to claim 1, wherein the dipping time in the step A) is 1-24 h; the mass ratio of the biomass containing the nitrogen compounds to the acid solution is as follows: 1: (0.4-2); the mass ratio of the sulfanilic acid to the isoamyl nitrite is 1: 3-3: 1.
4. the method according to claim 1, wherein the reaction temperature in step C) is 60 to 100 ℃; the reaction time is 4-24 h.
5. A biomass carbon-based solid acid catalyst, which is prepared by the preparation method of any one of claims 1 to 4.
6. A preparation method of 5-hydroxymethylfurfural comprises the following steps:
mixing glucose or fructose, a solvent and the catalyst prepared by the preparation method of any one of claims 1-4, stirring and reacting to obtain the 5-hydroxymethylfurfural.
7. The preparation method according to claim 6, wherein the reaction temperature is 80-250 ℃ and the catalytic dehydration time is 1-600 min.
8. A method for preparing furfural, comprising:
mixing xylose, a solvent and the catalyst prepared by the preparation method of any one of claims 1 to 4, stirring and reacting to obtain furfural.
9. The application of the catalyst prepared by the preparation method according to any one of claims 1 to 4 in the preparation of 5-hydroxymethylfurfural or furfural.
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| CN109734722B (en) * | 2019-01-21 | 2021-08-24 | 中国科学院成都有机化学有限公司 | Method for preparing isosorbide by dehydrating sorbitol |
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