CN106866590B - A kind of method that biomass saccharide compound prepares 5- ethoxymethyl furfural - Google Patents
A kind of method that biomass saccharide compound prepares 5- ethoxymethyl furfural Download PDFInfo
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- -1 saccharide compound Chemical class 0.000 title claims abstract description 23
- 239000002028 Biomass Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 25
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 239000011973 solid acid Substances 0.000 claims abstract description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 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 description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims 1
- 238000010586 diagram Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 201000005402 Hermansky-Pudlak syndrome 2 Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000238370 Sepia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 101000985495 Staphylococcus saprophyticus subsp. saprophyticus (strain ATCC 15305 / DSM 20229 / NCIMB 8711 / NCTC 7292 / S-41) 3-hexulose-6-phosphate synthase 2 Proteins 0.000 description 1
- 101000985500 Staphylococcus saprophyticus subsp. saprophyticus (strain ATCC 15305 / DSM 20229 / NCIMB 8711 / NCTC 7292 / S-41) 3-hexulose-6-phosphate synthase 3 Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
- B01J31/064—Dendrimers
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/638—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of methods that biomass saccharide compound prepares 5- ethoxymethyl furfural, this method is using structural formula acid functionalization high molecular weight carbon materials as shown in Equation 1 as solid acid catalyst, one step of catalysis biomass saccharide compound is converted to 5- ethoxyl methyl furfural in ethanol, reaction temperature is 80~160 DEG C, the reaction time 2~for 24 hours；The present invention is using biomass saccharide compound as raw material, raw material sources are extensive, at low cost, catalytic reaction activity is high, 5- ethoxyl methyl furfural directly is converted by one step of raw material under acid functionalization high molecular weight carbon materials catalyst action, simple process and high income, up to 70% or more, acid functionalization high molecular weight carbon materials have the characteristics that high reaction activity, easily-activated and reusable, solve the problems, such as that cost of material is high, catalyst active and stability is insufficient and hardly possible recycles, conducive to popularization.
Description
Technical field:
The present invention relates to biomass-based high-grade chemicals synthesis technical fields, and in particular to a kind of biomass carbohydrate chemical combination
The method that object prepares 5- ethoxymethyl furfural.
Background technique:
In recent years, as sharply consumption and the mankind of fossil resource are to the growing of energy demand, Looking For Substitutions Of Oil
Become the hot spot of current research to reduce society to the dependence of petrochemicals.It is raw in numerous reproducible green energy resources
Substance is uniquely to can be used to produce high added value platform chemicals and offer energy consumption containing carbon resource.
Important component of the saccharide compound as biomass can generate a series of with specific function through acid catalyzed degradation
The platform chemicals of energy group, such as 5 hydroxymethyl furfural, succinic acid, glycerol and sorbierite.Wherein, 5 hydroxymethyl furfural conduct
A kind of important platform small molecule can be converted into again 5- ethoxyl methyl furfural (EMF), levulic acid, 2,5- furans dimethyl ether,
The high added values compound such as 2,5- furyl dimethyl carbinol, furandicarboxylic acid, maleic anhydride.In recent years, EMF is because with higher
Energy density (8.7kWh/L), it is close with the energy density of gasoline (8.8kWh/L) and diesel oil (9.7kWh/L), it is much higher than ethyl alcohol
Energy density (6.1kWh/L), while there is good oxidation stability and higher 16 octane number, it is considered to be a kind of
The liquid fuel of great potential.
Currently, EMF can not only be obtained in ethanol system through acid catalysed etherification by 5 hydroxymethyl furfural, but also can be by 5- hydroxyl first
Base furfural generates under highly basic effect with halohydrocarbons reaction.In addition, saccharide compound can also be under acid catalyst effect through isomery
One steps of processes such as change, dehydration, protonation, etherificate convert to obtain EMF.101400666 B of CN report is made using zeolite or inorganic acid
Catalyst by glucose and it is fructose converting be 5- ethoxyl methyl furfural, selectivity of product is 30% or so.CN102911141A
A kind of method for preparing 5- ethoxyl methyl furfural is disclosed, this method uses a series of heteropolyacid salts with structure with Keggin
Catalysis 5 hydroxymethyl furfural and ethyl alcohol are etherified to obtain 5- ethoxyl methyl furfural, but heteropolyacid salt is soluble in polar solvent, causes
Catalyst recycling is difficult, and brings product purification problem.102206198 A of CN 105330622 A and CN reports that microwave is auxiliary
Acid catalysis biomass sugar is helped to synthesize 5- (alkoxyl-methyl) furfural.At present EMF preparation process there are still use HMF make cost of material compared with
High, catalytic erosion is relatively strong, activity is lower, is not easily recycled, the problems such as stability is insufficient.Therefore, it develops novel, green, high
The catalysis material of effect prepares the emphasis that EMF is still current research for the conversion of biomass-based one step of saccharide compound.
Summary of the invention:
The object of the present invention is to provide a kind of methods that biomass saccharide compound prepares 5- ethoxymethyl furfural, to have
High-specific surface area (830~1650m2/ g) and high porous volume (0.43~1.79cm3/ g) acid functionalization high molecular weight carbon materials catalysis
One step Efficient Conversion of biomass saccharide compound prepares 5- ethoxyl methyl furfural, solves the work of cost of material height, catalyst
Property with stability is insufficient and difficult the problem of recycling.
The present invention is achieved by the following technical programs:
A kind of method that biomass saccharide compound prepares 5- ethoxymethyl furfural, this method are as shown in Equation 1 with structural formula
Have high-specific surface area (830~1650m2/ g) and high porous volume (0.43~1.79cm3/ g) acid functionalization high molecular weight carbon materials
As solid acid catalyst, one step of catalysis biomass saccharide compound is converted to 5- ethoxyl methyl furfural in ethanol, reaction
Temperature is 80~160 DEG C, the reaction time 2~for 24 hours；The monomer of the acid functionalization high molecular weight carbon materials is selected from benzene, 1,4- to two
Any one of benzyl chloride or biphenyl-benzyl dichloride, corresponding acid functionalization high molecular weight carbon materials are abbreviated as HPS-x respectively, HDS-x and
HBS-x, wherein x is the dosage of the acid functionalization reagent chlorosulfonic acid during acid functionalization, and chlorosulfonic acid is relative to macromolecule carbon materials
The dosage of material is in 1~4mL/g；The saccharide compound is in glucose, fructose, cellobiose, sucrose, synanthrin, cellulose
It is any；The mass concentration of the saccharide compound be 5~25%, catalyst relative to substrate biomass saccharide compound
Quality dosage be 5~40%；
Reference literature: JACS, 2014,136,9028；Appl.Catal.B, 2015,176-177,718, the acid function
Change high molecular weight carbon materials the preparation method is as follows: prepare the high molecular weight carbon materials with high-specific surface area and high porous volume first,
Then solid acid catalyst is obtained after carrying out acid functionalization with chlorosulfonic acid.
Beneficial effects of the present invention are as follows:
1. present invention synthesis has high-specific surface area (830~1650m2/ g) and high porous volume (0.43~1.79cm3/ g)
High molecular weight carbon materials make catalyst precarsor, are conducive to the contact of raw material and acidity of catalyst site in reaction process, catalysis reaction
It is active high, it can promote reaction raw materials rapid conversion.
2. the present invention is using biomass-based saccharide compound cheap, from a wealth of sources as raw material, through acid functionalization high score
The catalysis of sub- carbon material can a step be converted into EMF, simple process and high income, wherein product EMF yield reaches as high as 70% or more.
In short, the present invention, using biomass saccharide compound as raw material, raw material sources are extensive, at low cost, catalytic reaction activity
Height directly converts 5- ethoxyl methyl furfural, work for one step of raw material under acid functionalization high molecular weight carbon materials catalyst action
Skill is simple and high income, and up to 70% or more, acid functionalization high molecular weight carbon materials have high reaction activity, easily-activated and can weigh
The features such as utilizing again solves the problems, such as that cost of material is high, catalyst active and stability is insufficient and hardly possible recycles, conducive to pushing away
Extensively.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Prepare the preparation of embodiment 1:HPS-2
First with anhydrous FeCl3Make initiator, benzene monomer and dimethoxy are catalyzed in nitrogen atmosphere, dichloroethane solvent
Methane polymerization, then in 80 DEG C of condensing reflux 12h, obtained sepia solid is washed three times with methanol, and using methanol as solvent
Soxhlet type is for 24 hours, vacuum dried to obtain phenyl high molecular weight carbon materials, is consolidated after then carrying out acid functionalization with chlorosulfonic acid
Body acid catalyst, chlorosulfonic acid are 2mL/g relative to the dosage of high molecular weight carbon materials, and specific surface area of catalyst obtained is 845m2/
G, pore volume 0.44cm3/g。
Prepare the preparation of embodiment 2:HDS-2
With reference to preparation embodiment 1, the difference is that the monomer of the acid functionalization high molecular weight carbon materials is right selected from Isosorbide-5-Nitrae-
Benzyl dichloride, and do not need that dimethoxymethane is added, specific surface area of catalyst obtained is 852m2/ g, pore volume 1.50cm3/
g。
Prepare the preparation of embodiment 3:HBS-1
With reference to preparation embodiment 2, the difference is that the monomer of the acid functionalization high molecular weight carbon materials is biphenyl dichloro
Benzyl, and chlorosulfonic acid relative to high molecular weight carbon materials dosage in 1mL/g, specific surface area of catalyst obtained is 1235m2/ g, hole
Volume is 1.14cm3/g。
Prepare the preparation of embodiment 4:HPS-3, HPS-4
With reference to preparation embodiment 1, the difference is that chlorosulfonic acid is 3 or 4mL/g relative to the dosage of high molecular weight carbon materials.
Prepare the preparation of embodiment 5:HDS-4
With reference to preparation embodiment 2, the difference is that chlorosulfonic acid is 4mL/g relative to the dosage of high molecular weight carbon materials.
Prepare the preparation of embodiment 6:HBS-3, HBS-4
With reference to preparation embodiment 3, the difference is that chlorosulfonic acid is 3 or 4mL/g relative to the dosage of high molecular weight carbon materials.
Embodiment 1-6:
Fructose, ethyl alcohol are added in pressure pipe, the mass concentration range of raw material fructose (substrate) is 5~25%, then
It is added and is urged relative to the quality dosage of substrate in 5~40% HPS-x or HDS-x or HBS-x acid functionalization high molecular weight carbon materials
Agent, 80~160 DEG C of reaction temperature, revolving speed 600rpm, reaction time 2~for 24 hours, specific reaction condition is referring to table 1；It will after reaction
Pressure pipe is placed in fast cooling in ice water, and organic membrane filter separating catalyst, reaction solution is after the filtering of 0.22 micron membrane filter by gas
Phase chromatography is tested and analyzed, and is measured 5- ethoxyl methyl furfural (EMF) yield in product and is reached as high as 80.1% (referring to table
1)。
Analytical conditions for gas chromatography is as follows:
Chromatographic column: KB-5 capillary column (0.25 μm of the μ m of 30.0m × 0.32)；
Sampling volume: 0.2 μ L；
Carrier gas: N2, 75mL/min；
Detection program: 220 DEG C of injector temperature, 70 DEG C of post case initial temperature (0.5min), 15 DEG C/min of heating rate,
205℃(0.5min)。
Embodiment 7-15:
Reference implementation example 1-6, the difference is that raw material is different and the condition of other reactions is different, actual conditions referring to
Table 1.5- ethoxyl methyl furfural (EMF) yield is referring also to table 1 in product.
Table 1
Claims (1)
1. a kind of method that biomass saccharide compound prepares 5- ethoxymethyl furfural, which is characterized in that this method is with structural formula
Schematic diagram specific surface area as shown in Equation 1 is 830~1650m2/ g, pore volume are 0.43~1.79cm3The acid functionalization high score of/g
Sub- carbon material is as solid acid catalyst, one step Synthesis 5- ethoxyl methyl of catalysis biomass saccharide compound in ethanol
Furfural, reaction temperature are 80~160 DEG C, the reaction time 2~for 24 hours；The monomer of the acid functionalization high molecular weight carbon materials be selected from benzene,
Isosorbide-5-Nitrae-is abbreviated as HPS-x to any one of benzyl dichloride or biphenyl-benzyl dichloride, corresponding acid functionalization high molecular weight carbon materials respectively,
HDS-x and HBS-x, wherein x be acid functionalization reagent chlorosulfonic acid during acid functionalization relative to carbon material HPS, HDS and
The dosage of HBS, x is in 1~4mL/g range；The saccharide compound is selected from glucose, fructose, cellobiose, sucrose, synanthrin, fibre
Tie up any one of element；The mass concentration of the saccharide compound is 5~25%, and catalyst is relative to substrate biomass carbohydrate
The quality dosage for closing object is 5~40%；
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| CN201710083109.XA CN106866590B (en) | 2017-02-16 | 2017-02-16 | A kind of method that biomass saccharide compound prepares 5- ethoxymethyl furfural |
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