CN115155616B - Nanocellulose-based porous solid acid catalyst and preparation method and application thereof - Google Patents
Nanocellulose-based porous solid acid catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 239000011973 solid acid Substances 0.000 title claims abstract description 105
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 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 39
- 239000008103 glucose Substances 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 229920002678 cellulose Polymers 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000001913 cellulose Substances 0.000 claims abstract description 35
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 239000004964 aerogel Substances 0.000 claims abstract description 26
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 239000000017 hydrogel Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008188 pellet Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002159 nanocrystal Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 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
- 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 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
- 239000007848 Bronsted acid Substances 0.000 claims 3
- 239000002253 acid Substances 0.000 abstract description 47
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 31
- 239000002841 Lewis acid Substances 0.000 abstract description 23
- 150000007517 lewis acids Chemical class 0.000 abstract description 21
- 238000011068 loading method Methods 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 33
- 235000010980 cellulose Nutrition 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 238000001132 ultrasonic dispersion 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
- 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 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- -1 compound Lewis acid Chemical class 0.000 description 3
- 230000000694 effects Effects 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
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000005303 weighing 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
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 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
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005406 washing 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
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-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
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940089206 anhydrous dextrose Drugs 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052719 titanium 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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
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, wherein the solid acid catalyst is prepared by compounding two kinds of nano-celluloses to prepare hydrogel, preparing aerogel through tertiary butanol solvent exchange and freeze drying, preparing a carbon matrix through high-temperature carbonization, and carrying the carbon matrix through a sulfonation process and a Lewis acid loading processAnd (3) acid and Lewis acid to obtain the solid acid catalyst. The solid acid catalyst has a self-assembled rigid skeleton structure formed by physical crosslinking of two nanocellulose, has high specific surface area and rich acid carrying sites, and can further improve the glucose conversion rate and the yield of 5-hydroxymethylfurfural.
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 and a preparation method thereof, and application of the catalyst in catalyzing glucose to convert 5-hydroxymethylfurfural.
Technical Field
Biorefinery is of great importance in promoting sustainable development of the environment and energy economy conversion. 5-hydroxymethylfurfural (5-HMF) is the most predominant biomass refining platform compound and can be used for preparing a large number of industrial products with high added value. The preparation of 5-HMF by catalytic conversion of glucose as a substrate is the most promising technology for industrial development, wherein the acid density of the solid acid, the accessibility of the acid to the substrate and the type of the acid are the most critical for the conversion of glucose to 5-HMF, and the conversion efficiency of the whole reaction, the yield and purity of the product are determined. The acid catalyst is used for preparing 5-hydroxymethylfurfural (5-HMF) by catalyzing glucose to convert, and has the main effects of promoting isomerization of aldehyde glucose into ketoglucose, so that further dehydration reaction is facilitated, and the carbon-based solid acid is a heterogeneous solid catalyst which takes a carbon material as a framework and contains proton acid sites. 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 less acid loading sites, single proton acid type, small provided reaction activity area and low catalytic efficiency.
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 of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a nano cellulose-based solid acid catalyst, which takes biomass resource nano cellulose as a raw material, adopts a freeze drying method to prepare nano cellulose-based aerogel, and takes the nano cellulose-based aerogel as a carbon material carrier to obtain nano cellulose-based through carbonization and sulfonation processesA solid acid; then obtaining the product with +.>The nanocellulose-based solid acid catalyst with acid active site has excellent synergistic catalytic performance.
The invention provides a preparation method of a nano cellulose-based porous solid acid catalyst, which comprises the following steps:
s1, adding the CNF-CNC suspension into CaCl 2 Obtaining hydrogel pellets in the solution, then soaking the pellets in an organic solvent for solvent exchange, freeze-drying the obtained alcogel pellets to obtain aerogel, and carbonizing to obtain a porous carbon matrix;
s2, sulfonating the porous carbon matrix to obtain a loadA 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 (carrying 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 0.8 to 2.5wt%, preferably 1.2wt%.
Preferably, the concentration ratio of the Cellulose Nanofibrils (CNF) to the Cellulose Nanocrystals (CNC) in S1 is 1:5 to 5:1, and more preferably 1:3 to 3:1;
preferably, the CNF-CNC suspension cellulose nanofibrils of S1 are obtained by mixing a cellulose nanofibril suspension and a cellulose nanocrystalline suspension. During mixing, ultrasonic dispersion is used, 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 as described in S1 2 The concentration of (2) is 0.05 to 0.5M, more preferably 0.2M.
Preferably, the organic solvent in S1 is at least one of t-butanol, ethanol and acetone.
Preferably, the organic solvent S1 refers to an anhydrous solution of the organic solvent or a mixed solution of tertiary butanol and water, and the concentration is 15% -100%;
preferably, the heating temperature of the carbonization treatment 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 as described in S3 is prepared with S2The mass ratio of the acid solid acid is 0.25:1-0.75:1;
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 of S3 is prepared with S2The mass ratio of the acid solid acid is 0.15:1-0.6:1;
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 to 0.1g/mL, more preferably 0.02g/mL, and the concentration of the Ti source in the organic solvent is 0.005 to 0.01g/mL, more preferably 0.018g/mL.
Preferably, the volume mass ratio of the hydrochloric acid to the porous solid acid catalyst in the step S3 is 1-4 mL:1.0g, more preferably 2.0mL:1.0g.
Preferably, the time of the standing in S3 is 12 to 36 hours, more preferably 24 hours.
Preferably, the temperature of the heat treatment in S3 is 200-600 ℃, and the heating time is 3-8 h. Preferably, the temperature of the heat treatment in S3 is 300-500 ℃, and the heating time is 4-6 h.
The invention provides a nano cellulose based porous solid acid catalyst which is prepared by the method.
As described above, the present invention also provides the use of a nanocellulose-based porous solid acid catalyst in the reaction of catalyzing the conversion of glucose to prepare 5-HMF.
The invention also provides a method for preparing 5-HMF by catalyzing glucose to convert by using the nanocellulose-based porous solid acid catalyst, which comprises the following steps.
Mixing glucose solution with DMSO to obtain mixed solution, adding nanocellulose-based porous solid acid catalyst, and heating to convert glucose to prepare 5-HMF.
The concentration of the glucose solution is 30% -70%, the volume ratio of the glucose solution to DMSO is 3:1-1:3, the concentration of the catalyst in the mixed solution is 5% -30% by weight, the reaction temperature is 100-180 ℃, and the reaction time is 10-18h.
After the reaction, the catalyst is separated from the product by centrifugation, and the catalyst can be reused after regeneration.
The invention uses nano cellulose aerogel as the carbon matrix of the porous carbon-based solid acid catalyst, and uses cellulose from two plant sources such as nano filaments, nano crystals and the like in a compounding way, so that the invention has low raw material cost and wide sources, and is an ideal material for the carbon matrix. The physical entanglement and self aggregation of the nanofibrils are promoted by utilizing the crystal structure of the rigidity of the nanocrystals, a high-strength 3D porous fiber network is formed, the defect of lower rigidity of a carbon matrix material skeleton is overcome, the structure and the catalytic performance stability of the catalyst are improved, and the catalyst can be recycled. According to the invention, tertiary butanol is used for carrying out solvent exchange on the nano cellulose water dispersion, the fibril structure of the aerogel is well preserved, the specific surface area is obviously higher than that obtained by traditional freeze drying, the pore diameter of the nano cellulose aerogel is reduced, the pore structure and the surface reaction sites are enriched, the solid acid load is improved, and the solid acid load is simultaneously loadedAn acid and a Lewis acid, and the acid is a Lewis acid,can play a role in synergetic catalysis, and promote the catalytic reaction efficiency of preparing 5-HMF by glucose conversion. In addition, al and Ti in the catalyst exist in the form of polyvalent oxides on the surface of the solid acid catalyst, so that Lewis acid active reaction sites with different intensities are provided, and a plurality of reaction paths are provided for subsequent reactions for catalyzing glucose to dehydrate and convert 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 nanocellulose, and can be prepared by low-cost and simple ways, thereby greatly reducing the cost. According to the invention, the porous carbon material is constructed by preparing the nano cellulose aerogel as a carrier of the solid acid catalyst, the ultrahigh porosity and the specific surface area of the aerogel material are depended on, the provided acid loading sites are obviously more than those of the existing catalyst, the solid acid catalytic efficiency can be greatly improved, and the conversion rate of 5-HMF is required to be further researched and improved.
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 required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope representation image of a carbonized nanocellulose-based carbon matrix provided in example 1 of the present invention, from which it can be seen that the aerogel exhibits a similar three-dimensional fiber network structure, and meanwhile, contains a two-dimensional lamellar skeleton interspersed therein, and the network and the lamellar are mutually crosslinked to form a porous structure rich in the interior of the aerogel;
FIG. 2 is a scanning electron microscope representation image of a nanocellulose-based porous solid acid catalyst provided in example 1 of the present invention, the catalyst surface comprising a heterogeneous morphology of a plurality of irregularly shaped, relatively flat surface particles;
detailed description of the preferred embodiments
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified. The room temperature and unspecified temperature of the invention are 20-35 ℃.
Cellulose nanofibrils and cellulose nanocrystals were purchased from the company Tianjin wood-essence biotechnology limited;
anhydrous dextrose was purchased from Shanghai microphone Biochemical technologies Inc.
Method for measuring catalyst performance
1. Acid density determination of nanocellulose-based solid acids
(1) Sulfonic acid density
Accurately weighing 0.1g of the catalyst, placing the catalyst in a 50mL beaker, adding 20mL of 1M NaCl solution, ultrasonically oscillating the catalyst in an ultrasonic cleaning tank at 200W for 30min, filtering the catalyst 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 calculation formula of the sulfonic acid density is as follows:
wherein, the liquid crystal display device comprises a liquid crystal display device,sulfonic acid group density, mmol/g; c (C) NaOH The concentration of NaOH solution and mol/L; v (V) NaOH For titration of the volume of NaOH solution used, mL; and m is the mass of the catalyst and g.
(2) Density of carboxylic acid
Accurately weigh 0.1g of catalyst in a 50mL beaker and add 0.01M NaHCO 3 30mL of solution, ultrasonically oscillating for 30min in an ultrasonic cleaning tank at 200W, filtering by using a vacuum suction filtration device, transferring 10mL of filtrate into a conical flask, titrating with 0.01M HCl standard solution by taking bromocresol green-methyl red as an indicator, and after the filtrate changes from green to dark red, obtaining the dark redThe red solution was boiled in boiling water for 2min, the solution turned from dark red to green, cooled to room temperature and then titrated with 0.01M HCl standard solution until the solution turned dark red again.
The carboxylic acid density was calculated as:
wherein, the liquid crystal display device comprises a liquid crystal display device,sulfonic acid group and carboxyl group density, mmol/g; d (D) COOH Carboxyl density, mmol/g; c (C) HCl The concentration of HCl solution and mol/L; />Is NaHCO 3 Solution volume, mL; v (V) HCl To titrate the volume of HCl solution used, mL.
(3) Density of phenolic hydroxy acid
Accurately weighing 0.1g of the catalyst, placing the catalyst in a 50mL beaker, adding 30mL of 0.01M NaOH solution, ultrasonically oscillating the catalyst in an ultrasonic cleaning tank at 200W for 30min, filtering the catalyst 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 calculation formula of the density of the phenolic hydroxyl acid is as follows:
wherein, the liquid crystal display device comprises a liquid crystal display device,is the total acid group density, mmol/g; d (D) Ar-OH Is the density of phenolic hydroxyl groups, mmol/g.
(4) Lewis acid Density
Pyridine vacuum adsorption-fourier transform infrared spectroscopy (FT-IR): in-situ infrared method is adopted, a sample is pressed into a round uniform sheet with the diameter of 15mm under the pressure of 20KN under the irradiation of an infrared lamp, and the round uniform sheet is placed in a container with CaF 2 In situ pool of salt flakes and in less than 10 -4 The sample was activated under high vacuum at Torr for 1 hour, pyridine was adsorbed on the sample at room temperature, and desorption was performed at 423K, 473K and 573K for 30 minutes, and FT-IR spectra of the sample were recorded. The spectrum range is 4000cm -1 ～400cm -1 。
Acid density calculation: and subtracting the absorption peak of the sample from the IR spectrogram obtained by desorbing pyridine at different temperatures recorded by in-situ infrared by using a difference spectrum method to obtain the pyridine absorption peak. Integral 1450cm -1 The nearby peak area was quantitatively calculated for Lewis acid. The acid density was calculated using beer's law using the extinction coefficient defined by c.a. emmis.
The calculation formula of the Lewis acid density is as follows:
wherein D is Lewis Is Lewis acid density, mmol/g;1.42 is the extinction coefficient of Lewis acid, cm/. Mu.mol; IA is a Lewis acid characteristic peak (1450 cm) -1 ) Is a combined peak area of (a); r is the radius of the self-supporting tablet, cm; w is the mass of the tablet and mg.
2. Determination of catalytic 5-HMF conversion by ultraviolet spectrophotometry
The unreacted glucose concentration and the concentration of the generated 5-HMF in the reaction solution were measured and calculated by an ultraviolet spectrophotometer, and then the glucose conversion and the 5-HMF yield were calculated according to the following formulas:
wherein m is Initial glucose G is the mass of glucose in the glucose solution; m is m Residual glucose G is the mass of glucose remaining unconverted after the reaction is completed; m is m 5-HMF G is the mass of the 5-HMF prepared by the reaction.
Example 1: loadPreparation method of acid porous solid acid catalyst
Cellulose Nanofibrils (CNF) and Cellulose Nanocrystalline (CNC) suspensions of a certain concentration are mixed in water according to a mass ratio of 3:1 and the total concentration is 1.2wt%, and 180W ultrasonic dispersion treatment is used for 4 minutes to obtain 1.2wt% CNF-CNC suspension. Titration of CNF-CNC suspension to 0.2M CaCl 2 In the solution, the liquid drops are formed into hydrogel pellets, after the completion, the pellets are soaked in 75% tertiary butanol for solvent exchange, the solution is exchanged once every 24 hours, and water in the gel pellets is fully replaced by tertiary butanol. The obtained alcogel pellets are frozen and dried for 48 hours at the temperature of minus 60 ℃ to obtain the aerogel. Aerogel in N 2 Heating to 400 ℃ at a heating rate of 10 ℃/min in an atmosphere by using a tube furnace, and maintaining for 2 hours to obtain the nanocellulose-based carbon matrix, wherein a scanning electron microscope characterization image is shown in figure 1.
50mL of concentrated H was used at 150 ℃ 2 SO 4 The aerogel carbon matrix was sulphonated for 15h and then cooled to room temperature. Pouring the reacted solid-liquid mixture into 500mL deionized water slowly along the wall of a beaker at room temperature, and using hot deionized water>80 ℃ washing until SO is no longer detected in the wash water 4 2- And then drying the catalyst in an oven at 60 ℃ for 24 hours, and putting the obtained sulfonated solid acid catalyst into a dryer for standby.
Accurately weighing 0.4g of aluminum isopropoxide and 0.36g of isopropyl titanate, mixing with 20mL of ethanol, sequentially adding 1.0g of sulfonated solid acid catalyst and 2.0mL of HCl solution under magnetic stirring at 100rpm, and keeping magnetic forceStirred for 2h and then allowed to stand at room temperature for 24h. Drying in a blast drying oven at 60deg.C, taking out dry solid component, placing into a small tubular furnace, and adding into 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 5 hours. After cooling, taking out the sample, namely the Al/Ti compound with the load capacity of 20 percentAcid porous solid acid catalyst.
Introducing acidic groups (-SO) into the carbon matrix by sulfonation process 3 H) Al-Ti oxide is uniformly dispersed in the catalyst pores in an amorphous structure form through a Lewis acid introduction process, and the nano cellulose aerogel carbon matrix well retains the internal pore structure through carbonization and sulfonation acid process optimization, and a scanning electron microscope characterization image is shown in figure 2.
Example 2: loadPreparation method of Lewis acid porous solid acid catalyst
The procedure is as in example 1 except that a concentration of Cellulose Nanofibrils (CNF) and a Cellulose Nanocrystalline (CNC) suspension are mixed in a 1:1 mass ratio to a total concentration of 1.2%, all other operations being identical to example 1. Obtaining the CNF/CNC ratio of 1:1 in the nano cellulose carbon matrixAcid porous solid acid catalyst.
Example 3: loadPreparation method of acid/compound Lewis acid porous solid acid catalyst
The procedure is as in example 1 except that a concentration of Cellulose Nanofibrils (CNF) and a Cellulose Nanocrystalline (CNC) suspension are mixed in a mass ratio of 1:3 to a total concentration of 1.2%, all other operations being identical to example 1. Obtaining the CNF/CNC ratio of 1:3 in the nano cellulose carbon matrixAcid porous solid acid catalyst.
Comparative example 1: preparation method of cellulose nanofibrillar porous solid acid catalyst
The procedure is as in example 1 except that instead of using cellulose nanocrystals, only cellulose nanofibrils with a suspension concentration of 1.2% are used to prepare an aerogel carbon matrix, all other operations being identical to those of example 1. Obtaining carbon matrix as cellulose nanofibrilsAcid porous solid acid catalyst.
Comparative example 2: preparation method of cellulose nanocrystalline porous solid acid catalyst
The procedure is as in example 1 except that instead of using cellulose nanofibrils, only cellulose nanocrystals with a suspension concentration of 1.2% are used to prepare an aerogel carbon matrix, all other things being equal to example 1. Obtaining the carbon matrix as cellulose nanocrystallineAcid porous solid acid catalyst.
Comparative example 3: loadPreparation method of acid/alumina porous solid acid catalyst
The procedure is as in example 1 except that 0.8g of aluminum isopropoxide is accurately weighed and mixed with 20ml of ethanol without compounding the Ti source, and the other procedures are the same as in example 1. The loading was 20%Acid/alumina porous solid acid catalyst.
Comparative example 4: loadAcid/titanium oxide porousProcess for preparing solid acid catalyst
The procedure is as in example 1 except that 0.72g isopropyl titanate is accurately weighed and mixed with 20ml ethanol without compounding the Al source, and the other procedures are the same as in example 1. The loading was 20%Acid/titania porous solid acid catalysts.
Comparative example 5
Load onlyThe preparation method of the acid porous solid acid catalyst comprises the following steps:
cellulose Nanofibrils (CNF) and Cellulose Nanocrystalline (CNC) suspension with a certain concentration are mixed according to a mass ratio of 3:1 and the total concentration is 1.2%, and 180W ultrasonic dispersion treatment is used for 4 minutes to obtain 1.2% CNF-CNC suspension. Titration of CNF-CNC suspension to 0.2MCaCl 2 In the solution, the liquid drops are formed into hydrogel pellets, after the completion, the pellets are soaked in 75% tertiary butanol for solvent exchange, the solution is exchanged once every 24 hours, and water in the gel pellets is fully replaced by tertiary butanol. The obtained alcogel pellets are frozen and dried for 48 hours at the temperature of minus 60 ℃ to obtain the aerogel. Aerogel in N 2 The aerogel carbon substrate was heated to 400 ℃ using a tube furnace at a heating rate of 10 ℃/min under an atmosphere and maintained for 2 hours.
The carbonized aerogel carbon matrix was subjected to 50mL of concentrated H at 150 c 2 SO 4 Sulfonation was carried out at 140℃for 15 hours, and then cooled to room temperature. Pouring the reacted solid-liquid mixture into 500mL deionized water slowly along the wall of a beaker at room temperature, and using hot deionized water>80 ℃ washing until SO is no longer detected in the wash water 4 2- Drying in oven at 60deg.C for 24 hr to obtain loadPorous solid acid catalyst of acid.
Comparative example 6
A preparation method of a porous solid acid catalyst only loaded with Lewis acid is the same as that of example 1, except that sulfonation treatment of nanocellulose-based aerogel is not introduced, only the Lewis acid compounded by Al/Ti is loaded, and other operations are the same as those of example 1. And obtaining the supported Lewis acid porous solid acid catalyst.
Comparative example 7
The procedure is as in example 1 except that instead of nanocellulose, only microcrystalline cellulose with a suspension concentration of 1.2% is used to prepare the aerogel carbon matrix, all other things being equal to example 1. Obtaining microcrystalline cellulose as carbon matrixAcid porous solid acid catalyst.
Comparative example 8
The procedure is as in example 1 except that instead of nanocellulose, only chitosan with a suspension concentration of 1.2% is used to prepare the aerogel carbon matrix, all other operations being identical to those of example 1. Obtaining chitosan as carbon matrixAcid porous solid acid catalyst.
Comparative example 9
The procedure is as in example 1 except that instead of nanocellulose, only sisal slag with a suspension concentration of 1.2% is used to prepare an aerogel carbon matrix, all other operations being identical to those of example 1. Obtaining sodium alginate as carbon matrixAcid porous solid acid catalyst.
The solid acid catalysts obtained in examples 1 to 7 and comparative examples 1 to 5 were measured for the densities of the sulfonic acid, carboxylic acid and phenolic hydroxyl acid, and the measurement results are shown in Table 1:
TABLE 1 nanocellulose-based solid acid surface acid Density
Note that: different superscripts (a, b and c) in the same column indicate that the difference in time is significant at p <0.05
The total acid density of the solid acid catalyst is provided by carboxyl, hydroxyl, sulfonic groups introduced by sulfonation treatment, lewis acid introduced by a Lewis acid loading process and the like on the surface of a carbon matrix. As can be seen from comparative examples 1 and 6, the sulfonation process greatly increases the total acid content of the catalyst, and the hydroxyl group content is reduced and the carboxyl group content is increased due to the strong oxidizing property of the concentrated sulfuric acid during the sulfonation. The carbon-based solid acid prepared by using bacterial cellulose in the prior study has a sulfonic acid group content of 0.85mmol/g, the sulfonic acid group content introduced by the sulfonation process is similar to that of the solid acid catalyst, and compared with the total acid content of the 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 sulfonation process has higher total acid content. In the dehydration and conversion process of glucose, lewis acid and glucose are introducedAcid synergy plays an important role in promoting the reaction; the table data shows that loading Al-Ti oxide does not cause +.>The acid content is obviously reduced, and the method has guiding significance for the subsequent high-efficiency preparation of 5-HMF by using the solid acid catalyst.
The invention also provides an application of the nanocellulose-based porous solid acid catalyst in a reaction for preparing 5-HMF by catalyzing glucose to convert, which comprises the following specific implementation steps:
example 4: application of nanocellulose-based porous solid acid catalyst in catalytic preparation of 5-HMF (high-performance chemical reaction) reaction
Glucose and deionized water were mixed to give a 50% strength glucose solution, which was then mixed with DMSO in a 1:2 volume ratio, 20wt% of the solid acid catalyst prepared in example 1 was added, and the reaction was continued at 140℃for 14h. After the reaction, the catalyst is separated from the product by centrifugation, the unreacted glucose concentration and the generated 5-HMF concentration in the reaction liquid 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 in example 4 was conducted 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 in example 4 was conducted 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 same as in example 4 was conducted except 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 same as in example 4 was conducted except 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 in example 4 was conducted except that the solid acid catalyst prepared in comparative example 3 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 15
The same as in example 4 was conducted except that the solid acid catalyst prepared in comparative example 4 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 16
The same as in example 4 was conducted except 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 in example 4 was conducted except that the solid acid catalyst prepared in comparative example 6 was used instead of the solid acid catalyst prepared in example 1.
Comparative example 18
The same as in example 4 was conducted except 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 in example 4 was conducted 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 in example 4 was conducted except that the solid acid catalyst prepared in comparative example 9 was used instead of the solid acid catalyst prepared in example 1.
The catalytic performance in the reaction for preparing 5-HMF by catalyzing the conversion of glucose was measured and calculated by using the indexes such as the conversion of glucose and the yield of 5-HMF, and the results are shown in Table 2.
TABLE 2 reactivity of solid acid catalysts
The effect of the 5-HMF catalytic methods of comparative example 4 and comparative examples 10 and 11 is that the glucose conversion and 5-HMF yield are maximized when CNF to CNC ratio in the carbon matrix is 3:1, because the proper ratio of CNF to CNC cross-linking forms a uniform pore structure and excellent stability of the carbon matrix skeleton, providing a basis for high specific surface area, and exhibiting the best catalytic performance. The loading of Lewis acid further improved glucose conversion and 5-HMF yield, indicating that Lewis acid andthe acid synergistic catalysis can improve the catalytic performance of the catalyst for the reaction of preparing 5-HMF by glucose conversion.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. 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. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. The preparation method of the nanocellulose-based porous solid acid catalyst is characterized by comprising the following steps of:
s1, adding the CNF-CNC suspension into CaCl 2 Obtaining hydrogel pellets in the solution, then soaking the pellets in an organic solvent for solvent exchange, freeze-drying the obtained alcogel pellets to obtain aerogel, and carbonizing to obtain a porous carbon matrix, wherein CNF is cellulose nanofibrils and CNC is cellulose nanocrystalline;
s2, sulfonating the porous carbon matrix to obtain a porous solid acid catalyst loaded with Bronsted 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;
the total concentration of cellulose nanofibrils and cellulose nanocrystals in the CNF-CNC suspension is 1.2wt%, and the concentration ratio of CNF to CNC in S1 is 1:3-3:1.
2. The method according to claim 1, characterized in that:
s1 CaCl 2 The concentration of (2) is 0.05-0.5M; the organic solvent in S1 is at least one of tertiary butanol, ethanol and acetone; the organic solvent is an anhydrous solution of the organic solvent or a mixed solution of tertiary butanol and water, and the concentration of the organic solvent is 15% -100%.
3. The method according to claim 1, characterized in that:
s3, the Al source is at least one of aluminum powder, aluminum isopropoxide, aluminum sec-butoxide, aluminum oxide, aluminum chloride and aluminum nitrate;
the Ti source in the S3 is at least one of isopropyl titanate, butyl titanate, titanium oxide, titanium powder, titanium chloride and tetraalkyl titanate;
the mass ratio of the Al source to the Bronsted acid solid acid prepared by S2 is 0.25:1-0.75:1;
the mass ratio of the Ti source to the Bronsted acid solid acid prepared by S2 is 0.15:1-0.6:1.
4. The method according to claim 1, characterized in that:
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; the volume mass ratio of the hydrochloric acid to the porous solid acid catalyst in the step S3 is 1-4 mL:1.0g.
5. The method according to claim 1, characterized in that:
the heating temperature of the carbonization treatment is 150-800 ℃ and the heating time is 1-8 hours; s2, the temperature of sulfonation treatment is 100-200 ℃, and the sulfonation time is 10-20 hours; and S3, the temperature of the heat treatment is 200-600 ℃, and the heating time is 3-8 hours.
6. A nanocellulose-based porous solid acid catalyst prepared by the method of any one of claims 1-5.
7. The use of a nanocellulose-based porous solid acid catalyst in accordance with claim 6 in a reaction to catalyze the conversion of glucose to produce 5-HMF.
8. A process for the preparation of 5-HMF using the nanocellulose-based porous solid acid catalyst of claim 6 to catalyze the conversion of glucose, characterized by comprising the steps of:
mixing glucose solution with DMSO to obtain mixed solution, adding nanocellulose-based porous solid acid catalyst, and heating to convert glucose to prepare 5-HMF.
9. The method according to claim 8, wherein:
the concentration of the glucose solution is 30% -70%, the volume ratio of the glucose solution to the DMSO is 3:1-1:3, the concentration of the catalyst in the mixed solution is 5% -30% by weight, the reaction temperature is 100-180 ℃, and the reaction time is 10-18h.
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