CN115155616A - Nano cellulose base porous solid acid catalyst and preparation method and application thereof - Google Patents
Nano cellulose base porous solid acid catalyst and preparation method and application thereof Download PDFInfo
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- CN115155616A CN115155616A CN202210870062.2A CN202210870062A CN115155616A CN 115155616 A CN115155616 A CN 115155616A CN 202210870062 A CN202210870062 A CN 202210870062A CN 115155616 A CN115155616 A CN 115155616A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 239000011973 solid acid Substances 0.000 title claims abstract description 105
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 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 40
- 239000008103 glucose Substances 0.000 claims abstract description 40
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920002678 cellulose Polymers 0.000 claims abstract description 35
- 239000001913 cellulose Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 239000004964 aerogel Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- 238000006277 sulfonation reaction Methods 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002159 nanocrystal Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000017 hydrogel Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 32
- 239000002841 Lewis acid Substances 0.000 abstract description 22
- 150000007517 lewis acids Chemical class 0.000 abstract description 20
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 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 34
- 229960001031 glucose Drugs 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- 235000010980 cellulose Nutrition 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000008569 process Effects 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- -1 compound Lewis acid Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 229910018575 Al—Ti Inorganic materials 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
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- 230000018044 dehydration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MKNQNPYGAQGARI-UHFFFAOYSA-N 4-(bromomethyl)phenol Chemical compound OC1=CC=C(CBr)C=C1 MKNQNPYGAQGARI-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
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- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 150000003839 salts Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the technical field of heterogeneous catalysts, and provides a preparation method and application of a nano cellulose-based porous solid acid catalyst
Acid and Lewis acid to obtain the solid acid catalyst. The solid acid catalyst has a self-assembled rigid skeleton structure formed by physically crosslinking two types of nano-cellulose, has high specific surface area and rich acid-carrying sites, and can further improve the conversion rate of glucose and 5-And (4) yield of the hydroxymethyl furfural.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysts, relates to a carbon-based solid acid catalyst, and a preparation method and application thereof, and particularly relates to a nano cellulose-based solid acid catalyst, a preparation method thereof, and application of the catalyst in catalyzing glucose to convert 5-hydroxymethylfurfural.
Technical Field
Biorefinery is of great significance in promoting environmental sustainable development and energy economy conversion. 5-hydroxymethylfurfural (5-HMF) is the most important biomass refining platform compound and can be used for preparing a large amount of industrial products with high added value. The preparation of 5-HMF by solid acid catalytic conversion with glucose as a substrate is the technology with the most industrial development prospect, wherein the acid density of the solid acid, the reaction accessibility of the acid to the substrate and the type of the acid are the most critical for converting the 5-HMF by the glucose, and the conversion efficiency, the yield and the purity of the product of the whole reaction are determined. The acid catalyst is mainly used for promoting the isomerization of the aldehyde glucose into the ketone glucose in the preparation of the 5-hydroxymethylfurfural (5-HMF) by catalyzing the conversion of the glucose, so that the further dehydration reaction is facilitated, the carbon-based solid acid is a heterogeneous solid catalyst which takes a carbon material as a framework base and contains protonic acid sites, and the carbon-based solid acid is a good catalyst carrier generally due to the characteristics of various porous structures of porous carbon with high specific surface area, acid-base environment tolerance, low cost, easiness in acquisition, good recovery characteristics, strong hydrophobicity, low density and the like, and is an ideal catalyst for large-scale production of the 5-HMF at present. However, the carbon-based solid acid prepared by the prior art comprises ion exchange resin, polymer solid acid and solid acid obtained by carbonizing and sulfonating biomass, and has the problems of low catalytic efficiency, such as few acid loading sites, single type of protonic acid, small provided reaction active area and the like.
Disclosure of Invention
The invention mainly aims to provide a nano cellulose based porous solid acid catalyst, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a nano cellulose base solid acid catalyst, which is characterized in that nano cellulose serving as a biomass resource is used as a raw material, a freeze-drying method is adopted to prepare nano cellulose base aerogel, and the nano cellulose base aerogel serving as a carbon material carrier is subjected to carbonization and sulfonation processes to obtain nano cellulose base aerogel
A solid acid; then loading Al and Ti oxides to obtain the catalyst with
The nano cellulose base solid acid catalyst with acid active sites has excellent synergistic catalytic performance.
The invention provides a preparation method of a nano cellulose base porous solid acid catalyst, which comprises the following steps:
s1, adding CNF-CNC suspension into CaCl 2 Obtaining hydrogel spheres in the solution, then soaking the spheres in an organic solvent for solvent exchange, freezing and drying the obtained alcohol gel spheres to obtain aerogel, and carbonizing the aerogel to obtain a porous carbon matrix;
s2, sulfonating the porous carbon substrate to obtain a load
A porous solid acid catalyst of an acid;
s3, uniformly mixing an Al source, a Ti source and an organic solvent, sequentially adding the porous solid acid catalyst prepared in the step S2 and hydrochloric acid, uniformly mixing, standing, and performing heat treatment to obtain the nano cellulose-based porous solid acid catalyst (loaded with Al/Ti compound Lewis acid)
Acid porous solid acid catalyst).
Preferably, the total concentration of cellulose nanofibrils and cellulose nanocrystals in the CNF-CNC suspension is between 0.8 and 2.5wt%, preferably 1.2wt%.
Preferably, the concentration ratio of the Cellulose Nanofibrils (CNF) and the Cellulose Nanocrystals (CNC) in S1 is 1;
preferably, the CNF-CNC suspension cellulose nanofibrils of S1 are obtained by mixing a cellulose nanofibril suspension and a cellulose nanocrystal suspension. Ultrasonic dispersion is used during mixing, the power used for ultrasonic dispersion is 100-300W, more preferably 150-240W, and the dispersion time is 1-5 minutes, more preferably 1-3 minutes;
preferably, caCl described in S1 2 The concentration of (B) is 0.05 to 0.5M, more preferably 0.2M.
Preferably, the organic solvent in S1 is at least one of tert-butanol, ethanol and acetone.
Preferably, the organic solvent in S1 is an anhydrous solution of an organic solvent or a mixed solution of tert-butyl alcohol and water, and the concentration is 15-100%;
preferably, the heating temperature of the carbonization treatment of S1 is 150-800 ℃, and the heating time is 1-8 h; more preferably, the heating temperature of the carbonization treatment is 300-600 ℃, the heating time is 1-5 h, and the heating rate is 5-20 ℃/min; the carbonization treatment is preferably carried out in a tube furnace.
Preferably, the temperature of the sulfonation treatment of S2 is 100-200 ℃, and the sulfonation time is 10-20 h; the sulfonating agent used in the sulfonation treatment is concentrated sulfuric acid.
Preferably, the Al source in S3 is at least one of aluminum powder, aluminum isopropoxide, aluminum sec-butoxide, aluminum oxide, aluminum chloride and aluminum nitrate;
preferably, the Al source described in S3 is obtained from S2
The mass ratio of the acid solid acid is 0.25;
preferably, the Ti source in S3 is at least one of isopropyl titanate, butyl titanate, titanium oxide, titanium powder, titanium chloride and tetraalkyl titanate;
preferably, the Ti source described in S3 is obtained by reacting with S2
The mass ratio of the acid solid acid is 0.15;
preferably, the organic solvent in step S3 is at least one of ethanol, methanol, isopropanol and acetone. The concentration of the Al source in the organic solvent is 0.005-0.1 g/mL, more preferably 0.02g/mL, and the concentration of the Ti source in the organic solvent is 0.005-0.01 g/mL, more preferably 0.018g/mL.
Preferably, the volume mass ratio of the hydrochloric acid in the step S3 to the porous solid acid catalyst is 1-4 mL:1.0g, more preferably 2.0mL:1.0g.
Preferably, the standing time of S3 is 12 to 36 hours, and more preferably 24 hours.
Preferably, the temperature of the heat treatment of S3 is 200-600 ℃, and the heating time is 3-8 h. Preferably, the temperature of the heat treatment of S3 is 300-500 ℃, and the heating time is 4-6 h.
The invention provides a nano cellulose base porous solid acid catalyst which is prepared by the method.
As described above, the invention also provides the application of the nano cellulose based porous solid acid catalyst in the reaction for catalyzing the conversion of glucose to prepare 5-HMF.
The invention also provides a method for preparing 5-HMF by catalyzing the conversion of glucose by using the nano cellulose based porous solid acid catalyst, which comprises the following steps.
Mixing a glucose solution with DMSO to obtain a mixed solution, adding a nano cellulose base porous solid acid catalyst, and heating to convert glucose to prepare 5-HMF.
The concentration of the glucose solution is 30-70%, v/v, the volume ratio of the glucose solution to DMSO is 3.
After reaction, the catalyst is separated from the product by centrifugation, and the catalyst can be reused after regeneration.
The invention takes the nano cellulose-based aerogel as the carbon substrate of the porous carbon-based solid acid catalyst, and combines the cellulose of two plant sources such as nano fibrils and nano crystals, so that the cost of the raw materials is low, the source is wide, and the nano cellulose-based aerogel is an ideal material for the carbon substrate. The rigid crystal structure of the nanocrystalline is utilized to promote the physical entanglement and self-aggregation of the nano fibrils, a high-strength 3D porous fiber network is formed, the defect of low rigidity of a carbon matrix material framework is overcome, the stability of the structure and the catalytic performance of the catalyst is improved, and the catalyst is beneficial to the reutilization of the catalyst. The invention uses tertiary butanol to carry out the method for preparing the nanocellulose aqueous dispersionSolvent exchange, the fibril structure of the aerogel is well preserved, the specific surface area is obviously higher than that of the aerogel obtained by the traditional freeze drying, the aperture of the nano-cellulose aerogel is reduced, the abundant pore structure and the surface reaction sites of the nano-cellulose aerogel are utilized to improve the solid acid loading capacity, and simultaneously the solid acid loading capacity is loaded
The acid and the Lewis acid can play a role in concerted catalysis, and the catalytic reaction efficiency of preparing the 5-HMF by converting the glucose is improved. In addition, al and Ti in the catalyst exist on the surface of the solid acid catalyst in the form of multi-valence oxide, so that Lewis acid active reaction sites with different strengths are provided, and a plurality of reaction paths are provided for the subsequent reaction of catalyzing the glucose dehydration and conversion into 5-HMF.
By adopting the technical scheme, compared with the prior art, the invention has the remarkable advantages that:
the carrier material of the porous solid acid catalyst used in the catalytic reaction is biomass resource nano-cellulose, and can be prepared by a low-cost and simple way, so that the cost is greatly reduced. According to the invention, the porous carbon material is constructed by preparing the nano cellulose-based aerogel to serve as a carrier of the solid acid catalyst, and the supported acid sites provided by the nano cellulose-based aerogel are obviously more than those of the existing catalyst depending on the ultrahigh porosity and the specific surface area of the aerogel material, so that the solid acid catalysis efficiency can be greatly improved, and the improvement of the conversion rate of 5-HMF is to be further researched.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a scanning electron microscope characterization image of a nanocellulose-based carbon substrate carbonized according to example 1 of the present invention, from which it can be seen that an aerogel exhibits a similar three-dimensional fiber network structure, and also contains a two-dimensional lamellar skeleton interspersed therein, and the network and the lamellar skeleton are cross-linked to each other to form a rich porous structure inside the aerogel;
fig. 2 is a scanning electron microscope characterization image of the nanocellulose-based porous solid acid catalyst provided in example 1 of the present invention, in which the surface of the catalyst is a heterogeneous phase composed of a large number of particles with irregular shapes and relatively flat surfaces;
detailed description of the preferred embodiment
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased. The room temperature and the unspecified temperature are both 20-35 ℃.
Cellulose nanofibrils and cellulose nanocrystals were purchased from Tianjin xylem Biotech ltd;
anhydrous glucose was purchased from Shanghai Michelin Biotech, inc.
Method for measuring performance of catalyst
1. Acid density determination of nanocellulose-based solid acids
(1) Density of sulfonic acid
Accurately weighing 0.1g of catalyst, placing the catalyst in a 50mL beaker, adding 20mL of 1M NaCl solution, ultrasonically oscillating the catalyst in an ultrasonic cleaning tank for 30min at 200W, filtering the solution by using a vacuum filtration device, transferring 10mL of filtrate into a conical flask, and titrating the filtrate by using 0.01M NaOH standard solution.
The formula for calculating the density of sulfonic acid is as follows:
wherein,
the sulfonic acid group density is mmol/g; c NaOH The concentration is NaOH solution, mol/L; v NaOH The volume of NaOH solution used for titration, mL; m is the weight of the weighed catalyst, g.
(2) Carboxylic acid density
Accurately weighed 0.1g of catalyst was placed in a 50mL beaker and 0.01M NaHCO was added 3 30mL of the solution is ultrasonically oscillated for 30min at 200W in an ultrasonic cleaning tank, a vacuum filtration device is used for filtering, 10mL of filtrate is moved into a conical flask, bromocresol green-methyl red is used as an indicator, 0.01M HCl standard solution is used for titration, after the filtrate is changed from green to dark red, the dark red solution is placed into boiling water for boiling for 2min, the solution is changed from dark red to green, and after the solution is cooled to room temperature, 0.01M HCl standard solution is used for continuous titration until the solution is changed into dark red again.
The carboxylic acid density is calculated as:
wherein,
the density of sulfonic acid group and carboxyl group is mmol/g; d COOH Is carboxyl density, mmol/g; c HCl Is the concentration of HCl solution, mol/L;
is NaHCO 3 Volume of solution, mL; v HCl Volume of HCl solution used for titration, mL.
(3) Density of phenolic hydroxy acids
Accurately weighing 0.1g of catalyst, placing the catalyst in a 50mL beaker, adding 30mL of 0.01M NaOH solution, ultrasonically oscillating the catalyst in an ultrasonic cleaning tank for 30min at 200W, filtering the solution by using a vacuum filtration device, transferring 10mL of filtrate into a conical flask, and titrating the filtrate by using 0.01M HCl standard solution.
The density of the phenolic hydroxy acid is calculated by the formula:
wherein,
total acid group density, mmol/g; d Ar-OH The density of phenolic hydroxyl groups is mmol/g.
(4) Lewis acid density
Pyridine vacuum adsorption-fourier transform infrared spectroscopy (FT-IR): in-situ infrared adopts a self-supporting sheet method, a sample is pressed into a circular uniform sheet with the diameter of 15mm under the irradiation of an infrared lamp under the pressure of 20KN, and the circular uniform sheet is placed in a container with CaF 2 In situ pool of salt tablet, and in the range of less than 10 -4 The sample was activated under a high vacuum at an atmospheric pressure of Torr for 1 hour, pyridine was adsorbed on the sample at ordinary temperature, and the sample was desorbed at 423K, 473K and 573K for 30 minutes, and the FT-IR spectrum of the sample was recorded. The range of spectrograph is 4000cm -1 ～400cm -1 。
Calculating the acid density: and subtracting the absorption peak of the sample from the IR spectrogram obtained after desorbing pyridine at different temperatures by using in-situ infrared recording by using a difference spectrum method to obtain the pyridine absorption peak. Integral 1450cm -1 The area of the peak near the Lewis acid is quantitatively calculated. Acid density was calculated using beer's law using the extinction coefficient defined by c.a. emmis.
The formula for calculating the Lewis acid density is as follows:
wherein D is Lewis Is the Lewis acid density, mmol/g;1.42 is extinction coefficient of Lewis acid, cm/mu mol; IA is a Lewis acid characteristic peak (1450 cm) -1 ) Integrated peak area of (a); r is the radius of the self-supporting tablet, cm; w is the mass of the tablet, mg.
2. Ultraviolet spectrophotometry for determining conversion rate of catalytic 5-HMF
The concentration of unreacted glucose and the concentration of generated 5-HMF in the reaction solution were measured and calculated by an ultraviolet spectrophotometer, and then the glucose conversion rate and the yield of 5-HMF were calculated according to the following formulas:
wherein m is Initial glucose Mass of glucose in glucose solution, g; m is a unit of The rest of glucose Mass g of the remaining unconverted glucose after the reaction; m is 5-HMF Mass of 5-HMF prepared for the reaction, g.
Example 1: load with a spring element
Preparation method of acid porous solid acid catalyst
A concentration of Cellulose Nanofibril (CNF) and Cellulose Nanocrystal (CNC) suspensions was mixed in water at a total concentration of 1.2wt% in a mass ratio of 3. The CNF-CNC suspension was titrated to 0.2M CaCl 2 And (3) in the solution, enabling the liquid drops to form hydrogel spheres, soaking the spheres with 75% tert-butyl alcohol for solvent exchange after the completion, and replacing the solution every 24 hours to fully replace water in the gel spheres with tert-butyl alcohol. And (3) freezing and drying the obtained alcogel pellets for 48 hours at the temperature of-60 ℃ to obtain the aerogel. Adding aerogel in N 2 Heating to 400 ℃ at a heating rate of 10 ℃/min in a tubular furnace under an atmosphere, and keeping for 2 hours to obtain the nano cellulose base carbon matrix, wherein a scanning electron microscope characterization image is shown in figure 1.
50mL of concentrated H was used at 150 deg.C 2 SO 4 The aerogel carbon matrix was sulfonated for 15h and then cooled to room temperature. The solid-liquid mixture after reaction is slowly poured into 500mL of deionized water along the wall of the beaker at room temperature, and hot deionized water is used(>80 ℃) until no more SO is detected in the wash water 4 2- And then drying the sulfonated solid acid catalyst in an oven at 60 ℃ for 24 hours, and putting the sulfonated solid acid catalyst into a dryer for later use.
0.4g of aluminum isopropoxide and 0.36g of isopropyl titanate are weighed accurately and mixed with 20mL of ethanol, 1.0g of sulfonated solid acid catalyst and 2.0mL of HCl solution are added in sequence under magnetic stirring at 100rpm, magnetic stirring is maintained for 2h, and then standing is carried out at room temperature for 24h. Drying in 60 deg.C blast drying oven, taking out dried solid, placing into small tubular furnace, and heating in N 2 Under the protection of atmosphere, the temperature is raised to 400 ℃ at a heating rate of 10 ℃/min, and the temperature is kept for 5h. After cooling, the sample is taken out, namely the load is 20 percent
Acid porous solid acid catalyst.
Introduction of acidic groups (-SO) into a carbon matrix by sulfonation process 3 H) Al-Ti oxide is uniformly dispersed in catalyst pores in an amorphous structure form through a Lewis acid introduction process, the internal pore structure of the nano-cellulose aerogel carbon matrix is well reserved through carbonization and sulfonated acid process optimization, and a scanning electron microscope characterization image is shown in figure 2.
Example 2: load
Preparation method of Lewis acid porous solid acid catalyst
The same as example 1 except that a certain concentration of Cellulose Nanofibril (CNF) and Cellulose Nanocrystal (CNC) suspensions were mixed at a mass ratio of 1. Obtaining the nano-crystalline cellulose carbon matrix with the CNF to CNC ratio of 1
Acid porous solid acid catalyst.
Example 3: load
Preparation method of acid/compound Lewis acid porous solid acid catalyst
The same as example 1 except that a certain concentration of Cellulose Nanofibril (CNF) and Cellulose Nanocrystal (CNC) suspensions were mixed at a mass ratio of 1. Obtaining the nano-crystalline cellulose carbon matrix with the CNF to CNC ratio of 1
Acid porous solid acid catalyst.
Comparative example 1: preparation method of cellulose nanofibril porous solid acid catalyst
The same procedure as in example 1 was repeated except that, instead of using the cellulose nanocrystals, only the cellulose nanofibrils having a suspension concentration of 1.2% were used to prepare the aerogel carbon matrix, and the other operations were identical to those of example 1. Obtaining cellulose nanofibrils as a carbon matrix
Acid porous solid acid catalyst.
Comparative example 2: preparation method of cellulose nanocrystalline porous solid acid catalyst
The same as example 1, except that cellulose nanofibrils were not used, and only cellulose nanocrystals having a suspension concentration of 1.2% were used to prepare an aerogel carbon matrix, the other operations were identical to example 1. To obtain a material with a matrix of cellulose nanocrystals
Acid porous solid acid catalyst.
Comparative example 3: load with a spring element
Preparation method of acid/alumina porous solid acid catalyst
The difference from example 1 is that, instead of compounding Ti source, 0.8g of aluminum isopropoxide was weighed out accurately and mixed with 20ml of ethanol, and the other operations were identical to example 1. Obtaining a loading of 20%
Acid/alumina porous solid acid catalyst.
Comparative example 4: load
Preparation method of acid/titanium oxide porous solid acid catalyst
The difference from example 1 is that 0.72g of isopropyl titanate was accurately weighed and mixed with 20ml of ethanol without compounding an Al source, and the other operations were the same as example 1. Obtaining a loading of 20%
Acid/titania porous solid acid catalysts.
Comparative example 5
Load only
The preparation method of the acid porous solid acid catalyst comprises the following steps:
a concentration of Cellulose Nanofibril (CNF) and Cellulose Nanocrystalline (CNC) suspensions was mixed at a total concentration of 1.2% in a mass ratio of 3. The CNF-CNC suspension was titrated to 0.2MCaCl 2 And in the solution, the liquid drops are formed into hydrogel pellets, after the hydrogel pellets are soaked by 75 percent of tertiary butanol, the solvent exchange is carried out, the solution is exchanged every 24 hours, and the water in the gel pellets is fully replaced by the tertiary butanol. And (3) freezing and drying the obtained alcogel pellets for 48 hours at the temperature of-60 ℃ to obtain the aerogel. Adding aerogel in N 2 Heated to 400 ℃ under an atmosphere using a tube furnace at a heating rate of 10 ℃/min and held for 2h to obtain an aerogel carbon matrix.
The aerogel carbon carbide substrate was loaded at 150 ℃ with 50mL of concentrated H 2 SO 4 Sulfonation was carried out at 140 ℃ for 15h, and then cooling to room temperature. Slowly pouring the solid-liquid mixture after reaction into 500mL deionized water along the wall of a beaker at room temperature, and adding hot deionized water (C)>80 ℃ C.) washingUntil no more SO is detected in the wash water 4 2- Then drying the mixture for 24 hours in an oven at 60 ℃ to obtain the load
Porous solid acid catalyst of acids.
Comparative example 6
The preparation method of the Lewis acid-only supported porous solid acid catalyst is the same as that of the example 1, except that the sulfonation treatment of the nano cellulose-based aerogel is not introduced, only the Al/Ti compounded Lewis acid is supported, and other operations are the same as those of the example 1. Obtaining the Lewis acid loaded porous solid acid catalyst.
Comparative example 7
The same as example 1, except that, instead of using nanocellulose, only microcrystalline cellulose having a suspension concentration of 1.2% was used to prepare an aerogel carbon matrix, the other operations were identical to example 1. To obtain microcrystalline cellulose as the carbon matrix
Acid porous solid acid catalyst.
Comparative example 8
The same procedure as in example 1 was repeated except that, instead of using nanocellulose, only chitosan was used at a suspension concentration of 1.2% to prepare an aerogel carbon substrate, and the other operations were performed in accordance with example 1. Obtaining chitosan with carbon as matrix
Acid porous solid acid catalyst.
Comparative example 9
The same as example 1, except that, instead of using nanocellulose, only sisal dregs having a suspension concentration of 1.2% were used to prepare an aerogel carbon matrix, the other operations were identical to example 1. The obtained carbon matrix is sodium alginate
Acid porous solid acid catalyst.
The densities of sulfonic acid, carboxylic acid and phenol hydroxy acid of the solid acid catalysts obtained in examples 1 to 7 and comparative examples 1 to 5 were measured, and the results of the measurements are shown in table 1:
TABLE 1 nanocellulose-based solid acid surface acid Density
Note: different superscript letters (a, b and c) in the same column indicate significant differences when p <0.05
The total acid density of the solid acid catalyst is provided by carboxyl and hydroxyl on the surface of a carbon substrate, sulfonic acid groups introduced by sulfonation treatment, lewis acid introduced by a Lewis acid loading process and the like. Comparing example 1 with comparative example 6, it can be seen that the sulfonation process greatly increases the total acid content of the catalyst, and due to the strong oxidizing property of concentrated sulfuric acid during the sulfonation process, the hydroxyl content is reduced, and the carboxyl content is increased. In the existing research, carbon-based solid acid prepared by using bacterial cellulose has the sulfonic acid group content of 0.85mmol/g, the sulfonic acid group content introduced by the sulfonation process is similar to the sulfonic acid group content, and compared with the total acid content of a commercial catalyst such as Nafion R-1100 (1.13 mmol/g), H-ZSM-5 (0.62 mmol /), H-Mordenite (0.44 mmol /), the solid acid catalyst prepared by the method has higher total acid content. In the dehydration conversion process of glucose, lewis acid is introduced to
The acid synergistic effect plays an important role in promoting the reaction; the table data shows that the loading of Al-Ti oxide does not cause
The acid content is obviously reduced, and the method has guiding significance for efficiently preparing 5-HMF by using a solid acid catalyst subsequently.
The invention also provides an application of the nano cellulose based porous solid acid catalyst in a reaction for preparing 5-HMF by catalyzing glucose conversion, which comprises the following specific implementation steps:
example 4: application of nanocellulose-based porous solid acid catalyst in reaction for catalyzing and preparing 5-HMF
Mixing glucose and deionized water to obtain a 50% glucose solution, mixing the glucose solution with DMSO in a volume ratio of 1. After the reaction, the catalyst and the product are separated by centrifugation, the concentration of unreacted glucose and the concentration of generated 5-HMF in the reaction solution are measured and calculated by an ultraviolet spectrophotometer, and then the glucose conversion rate, the 5-HMF selectivity and the 5-HMF yield are calculated.
Comparative example 10
The same as example 4 except that the solid acid catalyst prepared in example 2 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 11
The same as example 4 except that the solid acid catalyst prepared in example 3 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 12
The difference from example 4 is that the solid acid catalyst prepared in comparative example 1 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 13
The difference from example 4 is that the solid acid catalyst prepared in comparative example 2 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 14
The same as example 4 except that the solid acid catalyst prepared in comparative example 3 was used in place of the solid acid catalyst prepared in example 1.
Comparative example 15
The same as example 4 except that the solid acid catalyst prepared in comparative example 4 was used in place of the solid acid catalyst prepared in example 1.
Comparative example 16
The difference from example 4 is that the solid acid catalyst prepared in comparative example 5 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 17
The same as example 4 except that the solid acid catalyst prepared in comparative example 6 was used in place of the solid acid catalyst prepared in example 1.
Comparative example 18
The difference from example 4 is that the solid acid catalyst prepared in comparative example 7 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 19
The same as example 4 except that the solid acid catalyst prepared in comparative example 8 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 20
The same as example 4 except that the solid acid catalyst prepared in comparative example 9 was used in place of the solid acid catalyst prepared in example 1.
The catalytic performance in the reaction of preparing 5-HMF by catalyzing the conversion of glucose is measured and calculated by indexes such as the conversion rate of glucose and the yield of 5-HMF, and the results are shown in Table 2.
TABLE 2 reactivity of solid acid catalysts
Comparing the effects of the 5-HMF catalytic processes of example 4 and comparative examples 10 and 11, it can be seen that the glucose conversion rate and the 5-HMF yield are highest when the CNF to CNC ratio in the carbon matrix is 3. The supported Lewis acid can further improve the glucose conversion rate and the 5-HMF yield, which indicates that the supported Lewis acid and the supported Lewis acid have the advantages of
The acid concerted catalysis can improve the catalytic performance of the catalyst for the reaction of preparing 5-HMF by converting glucose.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a nano cellulose based porous solid acid catalyst is characterized by comprising the following steps:
s1, adding the CNF-CNC suspension into CaCl 2 Obtaining hydrogel spheres in the solution, then soaking the spheres in an organic solvent for solvent exchange, freezing and drying the obtained alcohol gel spheres to obtain aerogel, and carbonizing the aerogel to obtain a porous carbon matrix;
s2, sulfonating the porous carbon substrate to obtain a load
A porous solid acid catalyst of an acid;
s3, uniformly mixing the Al source, the Ti source and the organic solvent, sequentially adding the porous solid acid catalyst prepared in the S2 and hydrochloric acid, uniformly mixing, standing, and performing heat treatment to obtain the nano cellulose based porous solid acid catalyst.
2. The method of claim 1, wherein:
the total concentration of the cellulose nanofibrils and the cellulose nanocrystals in the CNF-CNC suspension is 0.8-2.5 wt%; s1, the concentration ratio of CNF to CNC is 1.
3. The method of claim 1, wherein:
s1 the CaCl 2 The concentration of (A) is 0.05-0.5M; s1, the organic solvent is at least one of tert-butyl alcohol, ethanol and acetone; s1, the organic solvent is an anhydrous solution of the organic solvent or a mixed solution of tert-butyl alcohol and water, and the concentration is 15-100%.
4. The method of claim 1, wherein:
s3, the Al source is at least one of aluminum powder, aluminum isopropoxide, aluminum sec-butoxide, aluminum oxide, aluminum chloride and aluminum nitrate;
s3, the Ti source is at least one of isopropyl titanate, butyl titanate, titanium oxide, titanium powder, titanium chloride and tetraalkyl titanate;
s3 said Al source with S2
The mass ratio of the acid solid acid is 0.25;
s3 said Ti source and S2
The mass ratio of the acid solid acid is 0.15.
5. The method of claim 1, wherein:
the organic solvent in the step S3 is at least one of ethanol, methanol, isopropanol and acetone; the concentration of the Al source in the organic solvent is 0.005-0.1 g/mL; the concentration of the Ti source in the organic solvent is 0.005-0.01 g/mL; step S3, the volume mass ratio of the hydrochloric acid to the porous solid acid catalyst is 1-4 mL:1.0g.
6. The method of claim 1, wherein:
s1, the heating temperature of the carbonization treatment is 150-800 ℃, and the heating time is 1-8 h; s2, the temperature of the sulfonation treatment is 100-200 ℃, and the sulfonation time is 10-20 h; s3, the temperature of the heat treatment is 200-600 ℃, and the heating time is 3-8 h.
7. A nanocellulose-based porous solid acid catalyst obtained by the method of any one of claims 1 to 6.
8. Use of the nanocellulose-based porous solid acid catalyst according to claim 7 in reactions for the catalytic conversion of glucose to 5-HMF.
9. A method for preparing 5-HMF by catalyzing the conversion of glucose using the nanocellulose-based porous solid acid catalyst of claim 7, characterized by comprising the steps of:
mixing a glucose solution with DMSO to obtain a mixed solution, adding a nano cellulose base porous solid acid catalyst, and heating to convert glucose to prepare 5-HMF.
10. The method of claim 9, wherein:
the concentration of the glucose solution is 30-70%, v/v, the volume ratio of the glucose solution to DMSO is 3.
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