CN113333022A - Preparation method and application of bifunctional solid acid catalyst - Google Patents
Preparation method and application of bifunctional solid acid catalyst Download PDFInfo
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- CN113333022A CN113333022A CN202110550229.2A CN202110550229A CN113333022A CN 113333022 A CN113333022 A CN 113333022A CN 202110550229 A CN202110550229 A CN 202110550229A CN 113333022 A CN113333022 A CN 113333022A
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- 239000011973 solid acid Substances 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000001588 bifunctional effect Effects 0.000 title claims description 56
- 229920001221 xylan Polymers 0.000 claims abstract description 136
- 150000004823 xylans Chemical class 0.000 claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000005406 washing Methods 0.000 claims abstract description 60
- 238000001035 drying Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 28
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 28
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 26
- 239000008103 glucose Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 86
- 229910021641 deionized water Inorganic materials 0.000 claims description 86
- 239000000725 suspension Substances 0.000 claims description 86
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 71
- 238000000967 suction filtration Methods 0.000 claims description 48
- 239000000706 filtrate Substances 0.000 claims description 45
- 239000012065 filter cake Substances 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 15
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000005457 ice water Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims 2
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- -1 hydrogen ions Chemical class 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000011010 flushing procedure Methods 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 235000000346 sugar Nutrition 0.000 description 4
- 150000008163 sugars Chemical class 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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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Abstract
The invention relates to a preparation method and application of a difunctional solid acid catalyst, and belongs to the technical field of solid acid catalysts for polymerization reactions. The catalyst of the invention is a modified sulfonated-xylan polymer; the method takes xylan as a raw material, prepares xylan-based polymeric carbon, and obtains the product by sulfonation reaction, ion exchange, washing with distilled water and drying. The method is simple to operate, the preparation process is green and environment-friendly, the concentration of the prepared catalyst hydrogen ions is 2.3-2.5mmol/g, the use temperature is 130-200 ℃, the 5-hydroxymethylfurfural with the yield of 89.7% is prepared in the catalytic conversion of glucose to the maximum, and after 5 times of recycling, the yield is still not lower than 85%, so that the method is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a preparation method and application of a bifunctional solid acid catalyst.
Background
Biomass-based sugars are easy to prepare and inexpensive, for example: sucrose, fructose, glucose and starch, but their use is currently very limited. Based on the expectation that scientists can convert fossil feedstock into biomass feedstock, biomass-based sugars are attracting much attention because of its sustainability and low cost and ready availability, and therefore, the study of biomass-based sugars to develop valuable products is one of the major challenges in the future. Among the biomass-based sugars, glucose is a monosaccharide which is most widely distributed and abundant in nature, and 5-hydroxymethylfurfural is an important biomass-based platform compound and is an important intermediate of fine chemicals in chemical and medical science. Therefore, the method for converting the glucose into the 5-hydroxymethylfurfural has good application prospect and has important commercial value in the industries of medicine and food processing.
The catalyst for preparing 5-hydroxymethylfurfural from glucose at the present stage is usually liquid acid such as sulfuric acid, hydrochloric acid, phosphoric acid and the like, has high catalytic performance and quick reaction, but can generate serious polymerization side reaction and corrode equipment, generate a large amount of waste water to pollute the environment, and cannot be recycled. Compared with the traditional liquid acid, the solid acid catalyst has the advantages of mild reaction, recycling and the like. The reaction for preparing 5-hydroxymethylfurfural from glucose is mainly divided into two steps, the first step is that glucose is isomerized into fructose under the catalysis of Lewis acid, and the second step is that fructose is dehydrated to generate 5-hydroxymethylfurfural under the catalysis of Bronsted acid.
The invention relates to a bifunctional solid acid catalyst containing Bronsted acid and Lewis acid, which is applied to the reaction for preparing 5-hydroxymethylfurfural by catalyzing the catalytic conversion of glucose, the yield of 5-hydroxymethylfurfural with 89.7 percent is obtained to the maximum extent, and after 5 times of recycling, the yield is still not lower than 85 percent, so that the catalyst is suitable for industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a bifunctional solid acid catalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the bifunctional solid acid catalyst is characterized by comprising the following steps of:
(1) adding 10-50 parts by mass of xylan into 50-100 parts by mass of deionized water, stirring at normal temperature for 0.5-2 hours, and performing suction filtration to obtain washed xylan; washing three times according to the method;
(2) stirring the washed xylan in 50-100 parts by mass of alcohol for 0.5-2h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan;
(3) adding 10-30 parts by mass of treated xylan into 50-60 parts by mass of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 1-10 parts by mass of concentrated sulfuric acid and 0.1-1 part by mass of chlorosulfonic acid into the suspension, and stirring vigorously; after the addition, putting the suspension into a high-pressure reaction kettle, filling 1-5MPa of gas into the kettle, and carrying out sulfonation reaction at 220 ℃ for 4-12h;
(4) carrying out suction filtration on the sulfonated product, washing the sulfonated product with methanol until the filtrate is clear, then washing the sulfonated product with deionized water until the pH of the filtrate is =6-7, and drying the filter cake for 12h at the temperature of 100 ℃ to obtain sulfonated xylan-based solid acid;
(5) taking 5-10 parts by mass of xylan-based solid acid, adding 100-150 parts by mass of deionized water and 0.1-5 parts by mass of inorganic iron salt, fully stirring for 10min, carrying out water bath at 70-90 ℃, and carrying out condensation reflux for 4-10 h;
(6) and (3) carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain the Fe-xylan-based bifunctional catalyst serving as the bifunctional solid acid catalyst.
The preparation method of the bifunctional solid acid catalyst is characterized in that the alcohol in the step (2) is one of methanol, ethanol and glycol.
The preparation method of the bifunctional solid acid catalyst is characterized in that the gas in the step (3) is one of nitrogen and carbon dioxide.
The preparation method of the bifunctional solid acid catalyst is characterized in that the inorganic ferric salt in the step (5) is one of ferric chloride, ferric sulfate, ferric nitrate and ferric acetylacetonate.
The application of the bifunctional solid acid catalyst according to claim 1, wherein the bifunctional solid acid catalyst is applied to a reaction for catalyzing catalytic conversion of glucose to prepare 5-hydroxymethylfurfural. Adding 1-5 parts by mass of glucose into 10-100 parts by mass of deionized water and 0.01-0.5 part by mass of catalyst, charging 1-6MPa of nitrogen, reacting at 190 ℃ for 2-6h, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of 5-hydroxymethylfurfural.
The preparation method of the invention has the following advantages and beneficial effects:
the invention relates to a bifunctional solid acid catalyst containing Bronsted acid and Lewis acid, which is applied to the reaction for preparing 5-hydroxymethylfurfural by catalyzing the catalytic conversion of glucose, the yield of 5-hydroxymethylfurfural with 89.7 percent is obtained to the maximum extent, and after 5 times of recycling, the yield is still not lower than 85 percent, so that the catalyst is suitable for industrial production.
Drawings
FIG. 1 is a flow diagram of the preparation of a bifunctional solid acid catalyst.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Comparative example 1
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering the sulfonated product, washing with methanol until the filtrate is clear, then washing with deionized water until the pH of the filtrate is =6-7, and drying the filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid;
adding 2g of glucose, 20g of deionized water and 0.05g of sulfonated xylan-based solid acid into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) on the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 25.4%.
Comparative example 2
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing for three times according to the method, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12 hours, and cooling to room temperature to obtain the treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering the sulfonated product, washing with methanol until the filtrate is clear, then washing with deionized water until the pH of the filtrate is =6-7, and drying the filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid;
adding 2g of glucose, 20g of deionized water and 0.05g of sulfonated xylan-based solid acid into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 10.5%.
Comparative example 3
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering the sulfonated product, washing with methanol until the filtrate is clear, then washing with deionized water until the pH of the filtrate is =6-7, and drying the filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 5g of ferric chloride, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 31.2%.
Comparative example 4
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing for three times according to the method, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12 hours, and cooling to room temperature to obtain the treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition is finished, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering and washing a sulfonated product with methanol until a filtrate is clear, then washing with deionized water until the filtrate has a pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, and calculating the hydrogen ion concentration of the xylan-based solid acid to be 2.45mmol/g by using an excess titration method; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.2 g of ferric chloride, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 29.2%.
Example 1
Adding 50g of xylan into 100g of deionized water, stirring at normal temperature for 2 hours, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 2 hours, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12 hours, and cooling to room temperature to obtain treated xylan; adding 30 g of treated xylan into 60 g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 10g of concentrated sulfuric acid and 0.1g of chlorosulfonic acid into the suspension, and violently stirring; and after the addition, putting the suspension into a high-pressure reaction kettle, flushing 5MPa of carbon dioxide into the kettle, sulfonating for 4 hours at 220 ℃, filtering the sulfonated product, washing the sulfonated product with methanol until the filtrate is clear, then washing the sulfonated product with deionized water until the pH of the filtrate is =6-7, and drying the filter cake for 12 hours at 100 ℃ to obtain the sulfonated xylan-based solid acid. Taking 10g of xylan-based solid acid, adding 150 g of deionized water and 3.9g of ferric chloride, fully stirring for 10min, carrying out water bath at 90 ℃, and carrying out condensation reflux for 4h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 5g of glucose, 100g of deionized water and 0.5g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 6MPa of nitrogen, reacting for 2 hours at 190 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 85.2%.
Example 2
Adding 15g of xylan into 50g of deionized water, stirring at normal temperature for 1 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 50g of methanol for 0.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 10g of treated xylan into 50g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 1g of concentrated sulfuric acid and 1g of chlorosulfonic acid into the suspension, and stirring vigorously; and after the addition, putting the suspension into a high-pressure reaction kettle, filling 1MPa of carbon dioxide into the kettle, sulfonating at 220 ℃ for 10 hours, carrying out suction filtration on a sulfonated product, washing with methanol until a filtrate is clear, then washing with deionized water until the pH of the filtrate is =6-7, and drying a filter cake at 100 ℃ for 12 hours to obtain the sulfonated xylan-based solid acid. Adding 100g of deionized water and 0.1g of ferric chloride into 5g of xylan-based solid acid, fully stirring for 10min, carrying out water bath at 70 ℃, and carrying out condensation reflux for 10h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 1g of glucose, 10g of deionized water and 0.01g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 1MPa of nitrogen, reacting for 6 hours at 130 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 78.4%.
Example 3
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition, putting the suspension into a high-pressure reaction kettle, filling 4 MPa of nitrogen into the kettle, sulfonating for 10 hours at 220 ℃, filtering and washing a sulfonated product with methanol until a filtrate is clear, then washing with deionized water until the pH of the filtrate is =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, and calculating the hydrogen ion concentration of the xylan-based solid acid to be 2.45mmol/g by using an excess titration method; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.2 g of ferric chloride, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 79.1%.
Example 4
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition is finished, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering and washing a sulfonated product with methanol until a filtrate is clear, then washing with deionized water until the filtrate has a pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, and calculating the hydrogen ion concentration of the xylan-based solid acid to be 2.45mmol/g by using an excess titration method; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.2 g of ferric chloride, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 89.7%.
Example 5
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of ethanol for 1 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 1g of concentrated sulfuric acid and 0.5g of chlorosulfonic acid into the suspension, and stirring vigorously; after the addition, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, carrying out suction filtration on a sulfonated product, washing with methanol until a filtrate is clear, then washing with deionized water until the filtrate pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.2 g of ferric chloride, fully stirring for 10 minutes, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 hours; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 83.5%.
Example 6
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of ethylene glycol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 0.8 g of concentrated sulfuric acid and 0.6 g of chlorosulfonic acid into the suspension, and stirring vigorously; after the addition, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, carrying out suction filtration on a sulfonated product, washing with methanol until a filtrate is clear, then washing with deionized water until the filtrate pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.2 g of ferric chloride, fully stirring for 10 minutes, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 hours; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 81.2%.
Example 7
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition is finished, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering and washing a sulfonated product with methanol until a filtrate is clear, then washing with deionized water until the filtrate has a pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, and calculating the hydrogen ion concentration of the xylan-based solid acid to be 2.45mmol/g by using an excess titration method; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.8g of ferric sulfate, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 82.1%.
Example 8
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition is finished, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering and washing a sulfonated product with methanol until a filtrate is clear, then washing with deionized water until the filtrate has a pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, and calculating the hydrogen ion concentration of the xylan-based solid acid to be 2.45mmol/g by using an excess titration method; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 3.5g of ferric nitrate, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of the 5-hydroxymethylfurfural to be 83.9%.
Example 9
Adding 10g of xylan into 70g of deionized water, stirring at normal temperature for 0.5 h, and performing suction filtration to obtain washed xylan; washing three times according to the method; stirring the washed xylan in 100g of methanol for 1.5 h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan; adding 20g of treated xylan into 40g of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 2g of concentrated sulfuric acid and 0.7 g of chlorosulfonic acid into the suspension, and violently stirring; after the addition is finished, putting the suspension into a high-pressure reaction kettle, flushing 4 MPa of carbon dioxide into the kettle, sulfonating for 10 hours at 220 ℃, filtering and washing a sulfonated product with methanol until a filtrate is clear, then washing with deionized water until the filtrate has a pH =6-7, drying a filter cake for 12 hours at 100 ℃ to obtain sulfonated xylan-based solid acid, and calculating the hydrogen ion concentration of the xylan-based solid acid to be 2.45mmol/g by using an excess titration method; taking 6 g of xylan-based solid acid, adding 120 g of deionized water and 1.2 g of ferric chloride, fully stirring for 10min, carrying out water bath at 80 ℃, and carrying out condensation reflux for 6 h; carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain a bifunctional solid acid catalyst Fe-xylan-based bifunctional catalyst;
adding 2g of glucose, 20g of deionized water and 0.05g of Fe-xylan-based bifunctional catalyst into a reaction kettle, charging 4 MPa of nitrogen, reacting for 4 hours at 160 ℃, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-Mass spectrometer) of the filtrate, and calculating the yield of 5-hydroxymethylfurfural. Washing the filter cake with ethanol for 5 times, putting into a vacuum oven, and drying at 50 ℃ for 12 h. And putting the dried catalyst into a reaction kettle again, and carrying out hydrogenation reaction according to the reaction conditions. After 5 cycles, the yield of 5-hydroxymethylfurfural was 85.8% (the conversions for 5 cycles were all 100%, the yields were 89.7%, 89.0%, 88.1%, 87.3%, 85.8%, respectively).
Claims (6)
1. The preparation method of the bifunctional solid acid catalyst is characterized by comprising the following steps of:
1) adding 10-50 parts by mass of xylan into 50-100 parts by mass of deionized water, stirring at normal temperature for 0.5-2 hours, and performing suction filtration to obtain washed xylan; washing three times according to the method;
2) stirring the washed xylan in 50-100 parts by mass of alcohol for 0.5-2h, performing suction filtration, putting the filter cake into a vacuum oven at 50 ℃ for drying for 12h, and cooling to room temperature to obtain treated xylan;
3) adding 10-30 parts by mass of treated xylan into 50-60 parts by mass of deionized water, stirring to form uniform suspension, placing the suspension in an ice water bath, slowly adding 1-10 parts by mass of concentrated sulfuric acid and 0.1-1 part by mass of chlorosulfonic acid into the suspension, and stirring vigorously; after the addition, putting the suspension into a high-pressure reaction kettle, filling 1-5MPa of gas into the kettle, and carrying out sulfonation reaction at 220 ℃ for 4-12h;
4) carrying out suction filtration on the sulfonated product, washing the sulfonated product with methanol until the filtrate is clear, then washing the sulfonated product with deionized water until the pH of the filtrate is =6-7, and drying the filter cake for 12h at the temperature of 100 ℃ to obtain sulfonated xylan-based solid acid;
5) taking 5-10 parts by mass of xylan-based solid acid, adding 100-150 parts by mass of deionized water and 0.1-5 parts by mass of inorganic iron salt, fully stirring for 10min, carrying out water bath at 70-90 ℃, and carrying out condensation reflux for 4-10 h;
6) and (3) carrying out suction filtration on the condensed and refluxed suspension, fully washing the suspension by deionized water, and drying a filter cake to obtain the Fe-xylan-based bifunctional catalyst serving as the bifunctional solid acid catalyst.
2. The method for preparing a bifunctional solid acid catalyst according to claim 1, wherein the alcohol in step (2) is one of methanol, ethanol, and ethylene glycol.
3. The method for preparing a bifunctional solid acid catalyst according to claim 1, wherein the gas in step (3) is one of nitrogen and carbon dioxide.
4. The method for preparing a bifunctional solid acid catalyst according to claim 1, wherein the inorganic ferric salt in step (5) is one of ferric chloride, ferric sulfate and ferric nitrate.
5. The application of the bifunctional solid acid catalyst according to claim 1, wherein the bifunctional solid acid catalyst is applied to a reaction for catalyzing catalytic conversion of glucose to prepare 5-hydroxymethylfurfural.
Adding 6.1-5 parts by mass of glucose into 10-100 parts by mass of deionized water and 0.01-0.5 part by mass of catalyst, charging 1-6MPa of nitrogen, reacting at 190 ℃ for 2-6h, cooling to room temperature, filtering, measuring GC-MS (gas chromatography-mass spectrometry) of the filtrate, and calculating the yield of 5-hydroxymethylfurfural.
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