CN115301242B - Catalyst for preparing 2, 5-dimethyl furan from glucose and preparation method thereof - Google Patents
Catalyst for preparing 2, 5-dimethyl furan from glucose and preparation method thereof Download PDFInfo
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- CN115301242B CN115301242B CN202210878078.8A CN202210878078A CN115301242B CN 115301242 B CN115301242 B CN 115301242B CN 202210878078 A CN202210878078 A CN 202210878078A CN 115301242 B CN115301242 B CN 115301242B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 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 title claims abstract description 33
- 239000008103 glucose Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 30
- 230000001588 bifunctional effect Effects 0.000 claims description 25
- 239000000084 colloidal system Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 229920000428 triblock copolymer Polymers 0.000 claims description 11
- 239000004246 zinc acetate Substances 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 abstract description 16
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 16
- 229930091371 Fructose Natural products 0.000 abstract description 11
- 239000005715 Fructose Substances 0.000 abstract description 11
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 9
- 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 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 53
- 239000000203 mixture Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000012018 catalyst precursor Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 239000008399 tap water Substances 0.000 description 10
- 235000020679 tap water Nutrition 0.000 description 10
- 229960000583 acetic acid Drugs 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000012362 glacial acetic acid Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/64—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of preparation of 2, 5-dimethylfuran, and particularly relates to a catalyst for preparing 2, 5-dimethylfuran from glucose and a preparation method thereof. The catalyst can prepare 2, 5-dimethylfuran by taking glucose as a raw material by a one-step method, and solves the problems of high raw material price of 5-hydroxymethylfurfural when the 2, 5-dimethylfuran is prepared by taking 5-hydroxymethylfurfural as a raw material in the prior art, because the 5-hydroxymethylfurfural is difficult to obtain high purity by adopting modes such as extraction, distillation and the like, and the problems of high purification difficulty, high price and the like are caused; compared with fructose, glucose has lower price and wider source. The catalyst has L acid, B acid and hydrogenation active components, can realize the one-step glucose preparation of 2, 5-dimethylfuran, does not need to purify and extract the intermediate product 5-hydroxymethylfurfural, simplifies the process and shortens the preparation flow.
Description
Technical Field
The invention belongs to the technical field of preparation of 2, 5-dimethylfuran, and particularly relates to a catalyst for preparing 2, 5-dimethylfuran from glucose and a preparation method thereof.
Background
With the increasing scarcity of petrochemical resources, and the environmental problems associated with use, renewable resources are being pursued to replace petrochemical resources for the production of liquid fuels and base chemicals. The biomass is a renewable resource with wide sources, and the preparation of liquid fuel and basic chemicals by using the biomass as raw materials meets the requirement of sustainable development, so that not only can human beings get rid of dependence on petrochemical resources, but also environmental problems such as greenhouse effect can be reduced.
2, 5-dimethyl furan (DMF for short) is liquid at normal temperature and has high energy density (30 kJ/cm) 3 ) High boiling point (92-94 ℃), high octane number (120 ℃) and excellent hydrophobicityThe water-based, explosion-proof and combustion-efficient additive is easy to transport and store, is considered as an excellent liquid fuel or gasoline additive, and is one of the alternative materials for replacing the traditional fossil energy. If the 2, 5-dimethylfuran can realize large-scale industrialized production, the problem caused by the large-scale use of fossil energy can be effectively solved.
In the prior art, fructose is generally used as a raw material, and 2, 5-dimethylfuran is prepared by a two-step method, (1) fructose is firstly converted into 5-hydroxymethylfurfural, and (2) 5-hydroxymethylfurfural is then converted into 2, 5-dimethylfuran. Although the two-step method can obtain very high yield of 2, 5-dimethylfuran, the two-step method has complex process and high energy consumption, and meanwhile, due to the high boiling point and poor thermal stability of 5-hydroxymethylfurfural, the 5-hydroxymethylfurfural is easily polymerized into humins or degraded into levulinic acid at high temperature and is easily dissolved in water and most of organic solvents, so that a proper extractant cannot be found for extraction to obtain the 5-hydroxymethylfurfural. Further, the source of glucose is more extensive than fructose, but if glucose is used as a raw material to prepare 2, 5-dimethylfuran, glucose is also required to be isomerized into fructose first, which further increases the difficulty of preparing 2, 5-dimethylfuran. Therefore, developing a catalyst which directly prepares 2, 5-dimethyl furan by taking glucose as a raw material has important significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, when fructose is used as a raw material to prepare 2, 5-dimethylfuran, 5-hydroxymethylfurfural is difficult to extract, fructose sources are limited, and if glucose is used as the raw material to prepare 2, 5-dimethylfuran, the process steps are complicated and the like, so that the catalyst for preparing 2, 5-dimethylfuran from glucose and the preparation method thereof are provided.
For this purpose, the invention provides the following technical scheme.
The invention provides a catalyst for preparing 2, 5-dimethylfuran from glucose, which comprises an acid-base bifunctional catalyst carrier and an active component;
the acid-base bifunctional catalyst carrier comprises a catalyst carrier intermediate and butyl tin dilaurate as raw materials;
the raw materials of the catalyst carrier intermediate comprise zinc salt, urea and a template agent;
the raw materials of the active component comprise copper salt.
The mass ratio of the zinc salt to the urea to the template agent is (1-20): (1-10): 1.
the mass ratio of the butyl tin dilaurate to the catalyst carrier intermediate is (0.1-1): 1.
the mass ratio of the copper salt to the acid-base bifunctional catalyst carrier is (0.05-0.5): 1;
preferably, the copper salt is at least one of copper nitrate, copper chloride and copper sulfate;
preferably, the template agent is at least one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and polyoxyethylene-polyoxypropylene block copolymer;
preferably, the zinc salt is at least one of zinc nitrate, zinc acetate, zinc chloride and zinc sulfate.
The invention also provides a preparation method of the catalyst, which comprises the following steps,
(1) Mixing zinc salt, urea and a template agent to form a colloid solution; crystallizing and roasting for the first time to obtain a catalyst carrier intermediate;
(2) Mixing dibutyltin dilaurate with the catalyst carrier intermediate obtained in the step (1), and performing second roasting to obtain an acid-base bifunctional catalyst carrier;
(3) And mixing the copper salt solution with the acid-base bifunctional catalyst carrier, and sequentially carrying out third roasting and fourth roasting.
In the step (3), the fourth roasting is performed under a hydrogen atmosphere;
preferably, the specific step of the fourth roasting comprises the steps of heating to 300-600 ℃ at a heating rate of 2-8 ℃/min and roasting for 2-5h.
The specific steps of the third roasting comprise the steps of heating to 400-800 ℃ at a heating rate of 1-10 ℃/min and roasting for 2-6h; preferably, the third firing is performed under an air atmosphere. Preferably, the temperature rise rate of the third firing is 5 ℃/min.
In the step (2), the specific step of the second roasting comprises the steps of heating to 200-1000 ℃ at a heating rate of 1-10 ℃/min and roasting for 2-8h. Preferably, the temperature rise rate is 5 ℃/min and the temperature of the second firing is 500 ℃.
In the step (1), the crystallization temperature is 80-150 ℃ and the crystallization time is 8-48h;
preferably, the specific step of the first roasting comprises the steps of heating to 300-800 ℃ at a heating rate of 1-20 ℃/min and roasting for 1-8 hours;
preferably, the first firing is performed under an air atmosphere.
The preparation method of the catalyst provided by the invention comprises the following steps,
(1) Mixing zinc salt, urea and a template agent, stirring to form a colloid solution, adjusting the pH of the colloid solution to about 4.5-5.5, crystallizing at 80-150 ℃ for 8-48h, and cooling to room temperature to obtain a precipitate; the precipitate is filtered and washed, dried for 4-48 hours at 60-120 ℃, and then heated to 300-800 ℃ at a heating rate of 1-20 ℃/min for first roasting for 1-8 hours to obtain the catalyst carrier intermediate. Wherein the first firing is performed under an air atmosphere.
(2) Dissolving dibutyltin dilaurate in a solvent, adding the catalyst carrier intermediate obtained in the step (1), stirring, drying at 60-120 ℃ for 4-48h, heating to 200-1000 ℃ at a heating rate of 1-10 ℃/min, and performing second roasting for 2-8h to obtain the acid-base bifunctional catalyst carrier; wherein the second firing is performed in an atmosphere of air.
(3) Mixing copper salt solution with the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying for 4-24h at 80-120 ℃, heating to 400-800 ℃ at a heating rate of 1-10 ℃/min, and performing third roasting for 2-6h to obtain a catalyst precursor, wherein the third roasting is performed in an air atmosphere; and heating the catalyst precursor to 300-600 ℃ at a heating rate of 2-8 ℃/min, and then performing fourth roasting to obtain the catalyst, wherein the fourth roasting time is 2-5h, the fourth roasting is performed under a hydrogen atmosphere, and the fourth roasting is performed through hydrogenation reduction reaction.
In addition, the invention provides a method for preparing 2, 5-dimethylfuran from glucose, a catalyst prepared by the preparation method, the method comprises the following steps,
glucose is mixed with the catalyst, reacted for 1-3 hours at 200-300 ℃, and cooled to obtain the 2, 5-dimethylfuran.
The reaction process for preparing DMF by a glucose one-step method is as follows:
the technical scheme of the invention has the following advantages:
1. the catalyst for preparing 2, 5-dimethylfuran from glucose can prepare 2, 5-dimethylfuran from glucose as a raw material by a one-step method, and solves the problems of high purification difficulty, high price and the like caused by the fact that the raw material of 5-hydroxymethylfurfural is expensive when the 2, 5-dimethylfuran is prepared from the 5-hydroxymethylfurfural as the raw material in the prior art, because the high purity of the 5-hydroxymethylfurfural is difficult to obtain by adopting modes such as extraction, distillation and the like; compared with fructose, glucose has lower price and wider source. The catalyst has L acid, B acid and hydrogenation active components, can realize the one-step glucose preparation of 2, 5-dimethylfuran, does not need to purify and extract the intermediate product 5-hydroxymethylfurfural, simplifies the process and shortens the preparation flow.
The zinc in the catalyst has a proper mesoporous structure, is favorable for the adsorption of reactants and the desorption of products, and also has an L acid site, so that glucose can be isomerized into fructose, and the blockage of a pore channel structure caused by the simultaneous loading of the catalyst on the B acid site and the L acid site is avoided; further, tin is introduced into the acid-base bifunctional catalyst carrier, the acid position B can be introduced, the dehydration of fructose is efficiently catalyzed to generate 5-hydroxymethylfurfural, and the active component copper can be subjected to hydrogenation reaction to convert the 5-hydroxymethylfurfural into 2, 5-dimethylfuran.
2. The catalyst for preparing 2, 5-dimethyl furan from glucose provided by the invention can regulate and control the catalytic activity and stability of the catalyst by controlling the dosage of raw materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a BET plot of the catalyst prepared in example 1 of the present invention;
FIG. 2 is a chart showing the distribution of copper elements of the catalyst prepared in example 1 of the present invention;
FIG. 3 is a view showing the recycling of the catalyst prepared in example 1 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a catalyst, which comprises the following steps,
(1) Accurately weighing 30g of zinc acetate, 5g of urea and 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and the hydrothermal kettle is placed into a 110 ℃ oven for crystallization for 24 hours; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a baking oven at 120 ℃ for 4 hours, fully grinding the precipitate, heating the precipitate to 500 ℃ at a heating rate of 5 ℃/min, and roasting the precipitate for 2 hours to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 2g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the catalyst carrier intermediate is fully stirred and then dried in an oven at 80 ℃ for 24 hours, and then the catalyst carrier is baked for 4 hours after the temperature is increased to 400 ℃ at the heating rate of 3 ℃/min, and the baking is carried out under the air atmosphere, so that the acid-base bifunctional catalyst carrier is obtained.
(3) Adding 2g of copper nitrate into water to prepare a solution, adding 12g of the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying in a 90 ℃ oven for 4 hours, heating to 600 ℃ at a heating rate of 5 ℃/min, and roasting for 2 hours to obtain a catalyst precursor, wherein the roasting is carried out under an air atmosphere; and then placing the catalyst precursor in a hydrogen atmosphere for hydrogenation reduction, heating to 450 ℃ at a heating rate of 5 ℃/min, and roasting for 4 hours to obtain the catalyst.
Fig. 1 is a BET diagram of the catalyst prepared in this example, and it can be seen from the BET diagram that the catalyst has an obvious mesoporous structure, and the mesopores provide a suitable pore structure for the reaction, which is favorable for the adsorption of the reactant and the desorption of the product, and meanwhile, the acid site of L can catalyze the isomerization of glucose to fructose.
FIG. 2 is a chart showing the distribution of copper elements in the catalyst prepared in this example. As can be seen from the Mapping graph, the copper elements are uniformly distributed in the catalyst.
FIG. 3 is a view showing the recycling of the catalyst prepared in this example. As can be seen from the figure, after four consecutive uses, the conversion of glucose and the yield of DMF did not significantly decrease. The catalyst provided by the invention has excellent reusability and good stability. Among them, the method for preparing DMF from glucose is referred to test example 1.
Example 2
The embodiment provides a preparation method of a catalyst, which comprises the following steps,
(1) Accurately weighing 40g of zinc acetate, 10g of urea and 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and the hydrothermal kettle is placed into a 90 ℃ oven for crystallization for 48 hours; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a 70 ℃ oven for 16 hours, fully grinding the precipitate, and then heating the precipitate to 700 ℃ at a heating rate of 10 ℃/min for roasting for 1 hour to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 4g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the mixture is fully stirred, the mixture is dried in a baking oven at 110 ℃ for 10 hours, then the mixture is heated to 200 ℃ at a heating rate of 6 ℃/min and then baked for 8 hours, and the baking is carried out under an air atmosphere, so that the acid-base bifunctional catalyst carrier is obtained.
(3) Adding 4g of copper nitrate into water to prepare a solution, adding 12g of the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying in an oven at 80 ℃ for 24 hours, heating to 500 ℃ at a heating rate of 3 ℃/min, and roasting for 6 hours to obtain a catalyst precursor; the catalyst precursor is put in hydrogen atmosphere for hydrogenation reduction, and is heated to 600 ℃ at the heating rate of 2 ℃/min and then baked for 2 hours to obtain the catalyst.
Example 3
The embodiment provides a preparation method of a catalyst, which comprises the following steps,
(1) Accurately weighing 10g of zinc acetate, 10g of urea and 5g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized for 8 hours in a 140 ℃ oven; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a baking oven at 100 ℃ for 6 hours, fully grinding the precipitate, heating the precipitate to 300 ℃ at a heating rate of 5 ℃/min, and roasting the precipitate for 8 hours to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 2g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the mixture is fully stirred, the mixture is dried for 24 hours in an oven at 80 ℃, and then the mixture is heated to 400 ℃ at a heating rate of 3 ℃/min and then baked for 4 hours, wherein the baking is carried out under an air atmosphere, and the acid-base bifunctional catalyst carrier is obtained.
(3) Adding 1g of copper sulfate into water to prepare a solution, adding 12g of the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying in a baking oven at 120 ℃ for 4 hours, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 2 hours to obtain a catalyst precursor; the catalyst precursor is put in hydrogen atmosphere for hydrogenation reduction, and is heated to 400 ℃ at the heating rate of 3 ℃/min and then baked for 5 hours to obtain the catalyst.
Example 4
The embodiment provides a preparation method of a catalyst, which comprises the following steps,
(1) Accurately weighing 30g of zinc acetate, 5g of urea and 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized in a baking oven at 110 ℃ for 24 hours; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in an oven at 80 ℃ for 48 hours, fully grinding the precipitate, heating the precipitate to 400 ℃ at a heating rate of 5 ℃/min, and roasting the precipitate for 6 hours to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 6g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the mixture is fully stirred, the mixture is dried for 24 hours in an oven at 80 ℃, and then the mixture is heated to 600 ℃ at a heating rate of 3 ℃/min and then baked for 3 hours, wherein the baking is carried out under an air atmosphere, and the acid-base bifunctional catalyst carrier is obtained.
(3) Adding 3g of copper nitrate into water to prepare a solution, adding 12g of the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying in a baking oven at 110 ℃ for 8 hours, heating to 700 ℃ at a heating rate of 1 ℃/min, and roasting for 5 hours to obtain a catalyst precursor; the catalyst precursor is put in hydrogen atmosphere for hydrogenation reduction, and is heated to 500 ℃ at the heating rate of 4 ℃/min and then baked for 3 hours to obtain the catalyst.
Example 5
The embodiment provides a preparation method of a catalyst, which comprises the following steps,
(1) Accurately weighing 30g of zinc acetate, 30g of urea and 30g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized in a baking oven at 120 ℃ for 36 hours; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a 110 ℃ oven for 24 hours, fully grinding the precipitate, and then heating the precipitate to 800 ℃ at a heating rate of 20 ℃/min for 2 hours to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 5g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the mixture is fully stirred, the mixture is dried for 24 hours in an oven at 80 ℃, and then the mixture is heated to 800 ℃ at a heating rate of 3 ℃/min and then baked for 5 hours, wherein the baking is carried out under an air atmosphere, so that the acid-base bifunctional catalyst carrier is obtained.
(3) Adding 6g of copper chloride into water to prepare a solution, adding 12g of the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying in a baking oven at 100 ℃ for 3 hours, heating to 800 ℃ at a heating rate of 5 ℃/min, and roasting for 2 hours to obtain a catalyst precursor; the catalyst precursor is put in hydrogen atmosphere for hydrogenation reduction, and is heated to 550 ℃ at the heating rate of 7 ℃/min and then baked for 3 hours to obtain the catalyst.
Example 6
The embodiment provides a preparation method of a catalyst, which comprises the following steps,
(1) Accurately weighing 30g of zinc acetate, 10g of urea and 5g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized for 8 hours in a baking oven at 150 ℃; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a 90 ℃ oven for 18 hours, fully grinding the precipitate, heating the precipitate to 700 ℃ at a heating rate of 15 ℃/min, and roasting the precipitate for 1 hour to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 1g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the mixture is fully stirred, the mixture is dried for 24 hours in an oven at 80 ℃, and then the mixture is heated to 1000 ℃ at a heating rate of 3 ℃/min and then baked for 2 hours, wherein the baking is carried out under an air atmosphere, and the acid-base bifunctional catalyst carrier is obtained.
(3) Adding 1g of copper nitrate into water to prepare a solution, adding 12g of the acid-base bifunctional catalyst carrier obtained in the step (2), stirring, drying in a 90 ℃ oven for 12 hours, heating to 700 ℃ at a heating rate of 3 ℃/min, and roasting for 4 hours to obtain a catalyst precursor; the catalyst precursor is put in hydrogen atmosphere for hydrogenation reduction, and is heated to 300 ℃ at a heating rate of 8 ℃/min and then baked for 5 hours to obtain the catalyst.
Comparative example 1
The comparative example provides a method for preparing a catalyst, comprising the following steps,
(1) Accurately weighing 30g of zinc acetate, 5g of urea and 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized in a baking oven at 110 ℃ for 24 hours; and taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a baking oven at 120 ℃ for 4 hours, fully grinding the precipitate, heating the precipitate to 500 ℃ at a heating rate of 5 ℃/min, and roasting the precipitate in an air atmosphere for 2 hours to obtain the catalyst.
Comparative example 2
The comparative example provides a method for preparing a catalyst, comprising the following steps,
(1) Accurately weighing 30g of zinc acetate, 5g of urea and 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized in a baking oven at 110 ℃ for 24 hours; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a baking oven at 120 ℃ for 4 hours, fully grinding the precipitate, heating the precipitate to 500 ℃ at a heating rate of 5 ℃/min, and roasting the precipitate for 2 hours to obtain a ZnO catalyst carrier intermediate; wherein the calcination is performed under an air atmosphere.
(2) 2g of dibutyltin dilaurate is dissolved in 50mL of acetone, 10g of the catalyst carrier intermediate is added, the catalyst carrier intermediate is fully stirred and then dried in an oven at 80 ℃ for 24 hours, the temperature is raised to 400 ℃ at the heating rate of 3 ℃/min, and then the catalyst is obtained after roasting for 4 hours under the air atmosphere.
Comparative example 3
The comparative example provides a method for preparing a catalyst, comprising the following steps,
(1) Accurately weighing 30g of zinc acetate, 5g of urea and 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, template agent), placing into a flask, adding 100mL of distilled water, and mechanically stirring at 45 ℃ for 2h to form a colloid solution; glacial acetic acid is added into the colloid solution, the pH is regulated to about 5.0, the mixture is moved into a 200mL hydrothermal kettle, and then the mixture is crystallized in a baking oven at 110 ℃ for 24 hours; taking out the hydrothermal kettle after crystallization, putting the hydrothermal kettle into tap water, cooling to room temperature to obtain a precipitate, filtering and washing the precipitate, drying the precipitate in a baking oven at 120 ℃ for 4 hours, fully grinding the precipitate, and then heating the precipitate to 500 ℃ at a heating rate of 5 ℃/min for 2 hours to obtain the ZnO catalyst carrier; wherein the calcination is performed under an air atmosphere.
(2) Adding 2g of copper nitrate into water to prepare a solution, adding 12g of the catalyst carrier, stirring, drying in a 90 ℃ oven for 4 hours, heating to 600 ℃ at a heating rate of 5 ℃/min, and roasting for 2 hours to obtain a catalyst precursor; the catalyst precursor is put in hydrogen atmosphere for hydrogenation reduction, and is heated to 450 ℃ at a heating rate of 5 ℃/min and then baked for 4 hours to obtain the catalyst.
Test examples
The test example provides an evaluation of the performance of the catalysts of the examples
The method for preparing 2, 5-dimethylfuran by glucose comprises the following steps: 1g of glucose, 30ml of tetrahydrofuran and 0.1g of catalyst (prepared in each example and comparative example) were added into a reaction kettle, the reaction kettle was sealed, the air in the kettle was replaced with hydrogen, 4MPa of hydrogen was introduced, and after stirring and heating to 220 ℃, the reaction was carried out for 2 hours, the reaction kettle was rapidly placed in tap water and cooled to room temperature, and the product was obtained.
The glucose conversion was measured by liquid chromatography and the yield of 2, 5-dimethylfuran was measured by gas chromatography, and the results are shown in Table 1.
TABLE 1
As can be seen from the contents in Table 1, the catalyst provided by the invention has good yield and selectivity of 2, 5-dimethylfuran when being used for preparing 2, 5-dimethylfuran from glucose.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The catalyst for preparing 2, 5-dimethyl furan from glucose is characterized by comprising an acid-base bifunctional catalyst carrier and an active component;
the acid-base bifunctional catalyst carrier comprises a catalyst carrier intermediate and butyl tin dilaurate as raw materials;
the raw materials of the catalyst carrier intermediate comprise zinc salt, urea and a template agent;
the raw materials of the active component comprise copper salt;
the preparation method of the catalyst comprises the following steps:
(1) Mixing zinc salt, urea and a template agent to form a colloid solution; crystallizing and roasting for the first time to obtain a catalyst carrier intermediate; wherein the specific steps of the first roasting include: heating to 300-800 ℃ at a heating rate of 1-20 ℃/min, and roasting for 1-8h;
(2) Mixing dibutyltin dilaurate with the catalyst carrier intermediate obtained in the step (1), and performing second roasting to obtain an acid-base bifunctional catalyst carrier; wherein the specific steps of the second roasting include: heating to 200-1000 ℃ at a heating rate of 1-10 ℃/min, and roasting for 2-8h;
(3) Copper salt solution is mixed with the acid-base bifunctional catalyst carrier and is subjected to third roasting and fourth roasting in sequence; wherein the specific steps of the third roasting comprise: heating to 400-800 ℃ at a heating rate of 1-10 ℃/min, and roasting for 2-6h; the specific steps of the fourth roasting include: heating to 300-600 ℃ at a heating rate of 2-8 ℃/min, and roasting for 2-5h.
2. The catalyst according to claim 1, characterized in that the mass ratio of zinc salt, urea and templating agent is (1-20): (1-10): 1.
3. the catalyst according to claim 1 or 2, characterized in that the mass ratio of the butyltin dilaurate to the catalyst support intermediate is (0.1-1): 1.
4. the catalyst according to claim 1 or 2, characterized in that the mass ratio of copper salt to acid-base bifunctional catalyst support is (0.05-0.5): 1.
5. The catalyst according to claim 1 or 2, wherein the copper salt is at least one of copper nitrate, copper chloride and copper sulfate;
the template agent is at least one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and polyoxyethylene-polyoxypropylene block copolymer;
the zinc salt is at least one of zinc nitrate, zinc acetate, zinc chloride and zinc sulfate.
6. The catalyst according to claim 1 or 2, wherein in the step (3), the fourth calcination is performed under a hydrogen atmosphere.
7. The catalyst according to claim 1 or 2, characterized in that the third calcination is carried out under an air atmosphere.
8. Catalyst according to claim 1 or 2, characterized in that the crystallization temperature is 80-150 ℃ for 8-48 hours.
9. The catalyst according to claim 1 or 2, characterized in that the first calcination is carried out under an air atmosphere.
10. A process for preparing 2, 5-dimethylfuran from glucose, characterized in that a catalyst according to any one of claims 1 to 9 is used, which comprises the steps of,
glucose is mixed with the catalyst, reacted for 1-3 hours at 200-300 ℃, and cooled to obtain the 2, 5-dimethylfuran.
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| CN102417493A (en) * | 2011-10-11 | 2012-04-18 | 浙江师范大学 | Method for preparing 2.5-dimethyl furan through glucose by adopting single-step method |
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| CN114736175A (en) * | 2022-03-09 | 2022-07-12 | 常州大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase |
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| CN105435800A (en) * | 2015-11-19 | 2016-03-30 | 中科合成油技术有限公司 | Catalyst used for preparing 2,5-methyl furan and preparation method thereof |
| CN112625012A (en) * | 2020-12-21 | 2021-04-09 | 中国科学院广州能源研究所 | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose with tin modified molecular sieve catalyst |
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