CN109776459A - A kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural - Google Patents
A kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural Download PDFInfo
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- hydroxymethyl furfural
- hydrophobic silica
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 88
- 239000011973 solid acid Substances 0.000 title claims abstract description 43
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229930091371 Fructose Natural products 0.000 title claims abstract description 25
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 25
- 239000005715 Fructose Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 16
- 230000018044 dehydration Effects 0.000 title claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 47
- 239000002105 nanoparticle Substances 0.000 claims abstract description 46
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 5
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- -1 alkyl trimethoxysilane Chemical compound 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 125000001165 hydrophobic group Chemical group 0.000 abstract 1
- 150000007524 organic acids Chemical group 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LKDRXBCSQODPBY-ZXXMMSQZSA-N alpha-D-fructopyranose Chemical compound OC[C@]1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-ZXXMMSQZSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- KYRNFTRJARVVEU-UHFFFAOYSA-N 5-hydroxy-3-methylfuran-2-carbaldehyde Chemical compound CC=1C=C(O)OC=1C=O KYRNFTRJARVVEU-UHFFFAOYSA-N 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910000540 VOPO4 Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The present invention relates to a kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural, step is the hydrophobic silica nanoparticle for preparing sulfhydrylation；Prepare the hydrophobic silica nanoparticle containing sulfite ion；Prepare hydrophobic solid acid；Hydrophobic solid acid catalysis fructose prepares 5 hydroxymethyl furfural.Using tetraethyl orthosilicate as silicon source, 3- mercaptopropyl trimethoxysilane is organic acid source, and the alkyl trimethoxysilane of different carbon chain lengths is hydrophobic group source, and hydrophobic solid acid is prepared through alkali cocondensation, oxidation and acidification step；The yield of HMF can achieve 88%.Compared with the prior art: the rehydrated side reaction of HMF can be effectively suppressed in this method, and green economy has good prospects for commercial application.
Description
Technical field
The invention belongs to biomass energy chemicals preparation technical fields, are specifically related to a kind of hydrophobic solid acid catalysis fruit
The method that sugared dehydration prepares 5 hydroxymethyl furfural.
Background technique
The development and utilization of biomass energy be various biomass materials are converted by different path for transformation it is high attached
The overall process of the environmental friendly products such as value added chemicals, biomaterial, oil product substitute.In recent years, it is with biomass
Raw material prepares high valuable chemicals, becomes one of research emphasis and the hot spot in biomass development and utilization field.
5 hydroxymethyl furfural is the important bridge for linking biomass and high valuable chemicals and fuel, therefore by biomass
It prepares 5 hydroxymethyl furfural to be of great significance, and is extensively and deeply studied.The dehydration of acid catalysis fructose is to prepare 5- hydroxyl
Methyl furfural most straightforward approach.The activity of acid catalyst is not only acid with it, the Nomenclature Composition and Structure of Complexes is related, but also by reaction condition
Such as solvent, the influence of time, temperature, especially reaction dissolvent.According to the literature, in high boiling organic solvent and ionic liquid
In body, it is commonly available higher 5 hydroxymethyl furfural yield and selectivity.But the use of high boiling organic solvent, make
The separating energy consumption for obtaining 5 hydroxymethyl furfural dramatically increases；Ionic liquid is expensive, limits its industrial applications；It is molten in green
In agent water, rehydrated reaction can occur for 5 hydroxymethyl furfural, and the yield and selectivity of 5 hydroxymethyl furfural are lower.
Up to the present, have yield and selectivity that several strategies improve 5 hydroxymethyl furfural in aqueous phase system.
Tian et al. (Carbonhydrate Research, 2012,351 (1): 35-41) reports one kind by water, Hydrophobic Ionic liquid
Body and solid acid VOPO4-SiO2The three-phase system of composition successfully inhibits 5 hydroxymethyl furfural by isolation solid acid and water
Rehydrated side reaction, improve the yield and selectivity of 5 hydroxymethyl furfural.But water contains in the dicyandiamide solution reported at present
Measure lower, and VOPO4With certain toxicity.Therefore, more efficient, more green catalyst system is developed to 5 hydroxymethyl furfural
Industrialized production have great importance.
In order to reduce the catalyst toxicity of prior art, improve the yield of 5 hydroxymethyl furfural and selection in aqueous phase system
Property, the present invention provides a kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural, the technical process
The high catalytic efficiency in aqueous phase reactions system, green economy.
Summary of the invention
It is an object of the present invention to provide a kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural, with
Improve yield and selectivity of the 5 hydroxymethyl furfural in aqueous phase system.
The present invention is to be realized by the following technical programs.
A kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural, it is characterised in that including following
Step:
(1) the hydrophobic silica nanoparticle of sulfhydrylation is prepared；
(2) the hydrophobic silica nanoparticle containing sulfite ion is prepared；
(3) hydrophobic solid acid is prepared；
(4) hydrophobic solid acid catalysis fructose prepares 5 hydroxymethyl furfural.
The step (1) prepare the hydrophobic silica nanoparticle of sulfhydrylation the preparation method is as follows: by ammonium hydroxide, just
Silester, long alkyl chains C3-C16Alkyl trimethoxysilane and 3- mercaptopropyl trimethoxysilane be dissolved in ethyl alcohol
In solution, 10-72h is stirred to react under the conditions of 40-60 DEG C, centrifugation, washing, drying obtain the hydrophobic of white precipitate sulfhydrylation
Property Nano particles of silicon dioxide, it is C which, which contains mercapto functional group and long alkyl chains,3-C16Hydrophobicity alkane
Base chain, such as attached drawing 1.
The ammonium hydroxide, tetraethyl orthosilicate, long alkyl chains C3-C16Alkyl trimethoxysilane and 3- mercapto propyl three
Content of the methoxy silane in every liter of ethanol solution be respectively 0.05-0.1 liter, 0.1-0.8 kilograms, 0.01-0.05 kilograms and
0.005-0.025 kilograms；
10-72h, stirring rate 100-800rpm are stirred to react under the conditions of be set forth in 40-60 DEG C.
The preparation method of the hydrophobic silica nanoparticle of step (2) preparation containing sulfite ion is such as
Under: the hydrophobic silica nanoparticle of the sulfhydrylation of step (1) preparation is immersed in hydrogen peroxide, every liter of hydrogen peroxide contains
The hydrophobic silica nanoparticle 10-100g of sulfhydrylation, is stirred at room temperature 2-24h, and centrifugation, washing, drying are obtained containing Asia
The hydrophobic silica nanoparticle of sulfate ion, the nanoparticle surface contain sulfite ion and long alkyl chains
For C3-C16Hydrophobic alkyl chain, such as attached drawing 2.
The step (3) prepare hydrophobic solid acid the preparation method is as follows: containing inferior sulfate radical for step (2) is obtained
The hydrophobic silica nanoparticle of ion is dispersed in the dilution heat of sulfuric acid of 0.1-1mol/L, contains sulfite ion
Hydrophobic silica nanoparticle content in every liter of dilution heat of sulfuric acid is 10-100g, and 2-24h is stirred at room temperature, is centrifuged, washes
It washs, dry, obtain hydrophobic solid acid, which is C rich in sulfonic group and long alkyl chains3-C16Hydrophobicity alkane
Base chain, such as attached drawing 3.
The method that step (4) the hydrophobic solid acid catalysis fructose prepares 5 hydroxymethyl furfural is as follows: by fructose, step
(3) hydrophobic solid acid made from is distributed to the H that volume ratio is 0.1:1-20:12In O/ dimethyl sulfoxide mixed solution, fructose
It is respectively 0.1-50mol and 0.5-50g with content of the hydrophobic solid acid in every liter of mixed solution, and in 80-150 DEG C,
It is stirred to react 0.5-12h under 100-500rpm revolving speed, obtains product 5 hydroxymethyl furfural.
The present invention provides a kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural, with existing skill
Art is compared and is had the advantage that
(1) the rehydrated side reaction of 5 hydroxymethyl furfural, 5- hydroxyl can be effectively suppressed in hydrophobic solid acid provided by the invention
Methyl furfural preparation efficiency is high；
(2) hydrophobic solid acid provided by the invention is nontoxic, simple and easy to get；
(3) present invention uses green solvent water, and economical and efficient is easy to operate, has potential industrial application value.
Detailed description of the invention
The structure chart of the hydrophobic silica nanoparticle of Fig. 1 sulfhydrylation；The hydrophobic silica nanometer of sulfhydrylation
The structure chart of particle: intermediate black ball is Nano particles of silicon dioxide, and mercapto functional group is contained on surface and long alkyl chains are
C3-C16Hydrophobic alkyl chain.
Fig. 2 contains the structure chart of the hydrophobic silica nanoparticle of sulfite ion；Contain sulfite ion
Hydrophobic silica nanoparticle structure chart: intermediate black ball be Nano particles of silicon dioxide, sulfurous is contained on surface
Acid ion and long alkyl chains are C3-C16Hydrophobic alkyl chain.
The structure chart of Fig. 3 hydrophobic solid acid.The structure chart of hydrophobic solid acid: intermediate black ball is silica
Nanoparticle, sulfonic group is contained on surface and long alkyl chains are C3-C16Hydrophobic alkyl chain.
Specific embodiment
In conjunction with the drawings and specific embodiments, the present invention is described in further detail, it should be noted that the present invention
It is not limited only to these embodiments:
Embodiment 1
(1) by 0.05 liter of ammonium hydroxide, 0.8 kilogram of ethyl orthosilicate, 0.05 kilogram of hexadecyl trimethoxy silane and 0.025
Kilogram 3- mercaptopropyl trimethoxysilane is dissolved in 1 liter of ethanol solution, is stirred to react 72h under the conditions of 60 DEG C, 800rpm, from
The heart, washing, drying obtain the hydrophobic silica nanoparticle of white precipitate sulfhydrylation.
(2) the hydrophobic silica nanoparticle of the sulfhydrylation of step (1) preparation is immersed in hydrogen peroxide, every liter double
Oxygen water contains the hydrophobic silica nanoparticle 100g of sulfhydrylation, is stirred at room temperature for 24 hours, and centrifugation, washing, drying are contained
There is the hydrophobic silica nanoparticle of sulfite ion, which contains sulfite ion and hexadecane
Base hydrophobic chain.
(3) the hydrophobic silica nanoparticle containing sulfite ion made from step (2) is dispersed in 1mol/
In the dilution heat of sulfuric acid of L, the hydrophobic silica nanoparticle containing sulfite ion contains in every liter of dilution heat of sulfuric acid
Amount is 100g, is stirred at room temperature for 24 hours, centrifugation, washing, dry, obtains hydrophobic solid acid, the solid acid surfaces rich in sulfonic group and
Cetyl hydrophobic chain.
(4) hydrophobic solid acid made from fructose, step (3) is distributed to the H that volume ratio is 20:12O/ dimethyl sulfoxide
In mixed solution, the content of fructose and hydrophobic solid acid in every liter of mixed solution is respectively 50mol and 50g, and in 150
DEG C, it is stirred to react 12h under 500rpm revolving speed, obtains product 5 hydroxymethyl furfural.Fructose converting rate 100%, 5 hydroxymethyl furfural
Yield 88%, 5 hydroxymethyl furfural selectivity 88%.
Embodiment 2
(1) by 0.1 liter of ammonium hydroxide, 0.1 kilogram of ethyl orthosilicate, 0.01 kilogram of propyl trimethoxy silicane and 0.005 kilogram
3- mercaptopropyl trimethoxysilane is dissolved in 1 liter of ethanol solution, and 10h is stirred to react under the conditions of 40 DEG C, 100rpm, be centrifuged,
Washing, drying, obtain the hydrophobic silica nanoparticle of white precipitate sulfhydrylation.
(2) the hydrophobic silica nanoparticle of the sulfhydrylation of step (1) preparation is immersed in hydrogen peroxide, every liter double
Oxygen water contains the hydrophobic silica nanoparticle 10g of sulfhydrylation, and 2h is stirred at room temperature, and centrifugation, washing, drying are contained
The hydrophobic silica nanoparticle of sulfite ion, which contains sulfite ion and propyl is dredged
Water chain.
(3) the hydrophobic silica nanoparticle containing sulfite ion made from step (2) is dispersed in
In the dilution heat of sulfuric acid of 0.1mol/L, the hydrophobic silica nanoparticle containing sulfite ion is molten in every liter of dilute sulfuric acid
Content is 10g in liquid, and 2h is stirred at room temperature, and centrifugation, washing, drying obtain hydrophobic solid acid, which is rich in sulfonic acid
Base and propyl hydrophobic chain.
(4) hydrophobic solid acid made from fructose, step (3) is distributed to the H that volume ratio is 0.1:12O/ dimethyl is sub-
In sulfone mixed solution, the content of fructose and hydrophobic solid acid in every liter of mixed solution is respectively 0.1mol and 0.5g, and in
80 DEG C, 0.5h is stirred to react under 100rpm revolving speed, obtains product 5 hydroxymethyl furfural.Fructose converting rate 53%, 5- methylol chaff
Aldehyde yield 41%, 5 hydroxymethyl furfural selectivity 77.3%.
Embodiment 3
(1) by 0.08 liter of ammonium hydroxide, 0.5 kilogram of ethyl orthosilicate, 0.03 kilogram of octyl trimethoxy silane and 0.015 kilogram
3- mercaptopropyl trimethoxysilane is dissolved in 1 liter of ethanol solution, is stirred to react under the conditions of 50 DEG C, 500rpm for 24 hours, centrifugation,
Washing, drying, obtain the hydrophobic silica nanoparticle of white precipitate sulfhydrylation.
(2) the hydrophobic silica nanoparticle of the sulfhydrylation of step (1) preparation is immersed in hydrogen peroxide, every liter double
Oxygen water contains the hydrophobic silica nanoparticle 50g of sulfhydrylation, and 12h is stirred at room temperature, and centrifugation, washing, drying are contained
The hydrophobic silica nanoparticle of sulfite ion, which contains sulfite ion and octyl is dredged
Water chain.
(3) the hydrophobic silica nanoparticle containing sulfite ion made from step (2) is dispersed in
In the dilution heat of sulfuric acid of 0.5mol/L, the hydrophobic silica nanoparticle containing sulfite ion is molten in every liter of dilute sulfuric acid
Content is 50g in liquid, and 12h is stirred at room temperature, and centrifugation, washing, drying obtain hydrophobic solid acid, which is rich in sulphur
Acidic group and octyl hydrophobic chain.
(4) hydrophobic solid acid made from fructose, step (3) is distributed to the H that volume ratio is 10:12O/ dimethyl sulfoxide
In mixed solution, the content of fructose and hydrophobic solid acid in every liter of mixed solution is respectively 10mol and 25g, and in 120
DEG C, it is stirred to react 6h under 300rpm revolving speed, obtains product 5 hydroxymethyl furfural.Fructose converting rate 68%, 5 hydroxymethyl furfural are received
Rate 53%, 5 hydroxymethyl furfural selectivity 77.9%.
The invention proposes utilize a kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural；?
It is described by live preferred embodiment, related technical personnel can obviously not depart from the content of present invention, spirit and scope
It is interior method described herein to be modified or appropriate changes and combinations, Lai Shixian the technology of the present invention.In particular, it should be pointed out that
All similar replacements and change are apparent to those skilled in the art, they are considered as being included in this hair
In bright spirit, range and content.
Claims (7)
1. a kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural, it is characterised in that including following step
It is rapid:
(1) the hydrophobic silica nanoparticle of sulfhydrylation is prepared；
(2) the hydrophobic silica nanoparticle containing sulfite ion is prepared；
(3) hydrophobic solid acid is prepared；
(4) hydrophobic solid acid catalysis fructose prepares 5 hydroxymethyl furfural.
2. the method as described in claim 1, it is characterized in that step (1) prepares the hydrophobic silica nanoparticle of sulfhydrylation
The preparation method is as follows: by ammonium hydroxide, ethyl orthosilicate, long alkyl chains C3-C16Alkyl trimethoxysilane and 3- mercapto third
Base trimethoxy silane is dissolved in ethanol solution, and 10-72h is stirred to react under the conditions of 40-60 DEG C, and centrifugation washs, is dry,
The hydrophobic silica nanoparticle of white precipitate sulfhydrylation is obtained, which contains mercapto functional group and alkyl
Chain length is C3-C16Hydrophobic alkyl chain.
3. method according to claim 2, it is characterized in that ammonium hydroxide, tetraethyl orthosilicate, long alkyl chains C3-C16Alkyl
The content of trimethoxy silane and 3- mercaptopropyl trimethoxysilane in every liter of ethanol solution is respectively 0.05-0.1 liter, 0.1-
0.8 kilogram, 0.01-0.05 kilograms and 0.005-0.025 kilograms.
4. method according to claim 2, it is characterized in that being stirred to react 10-72h under the conditions of 40-60 DEG C, stirring rate is
100-800rpm。
5. the method as described in claim 1, it is characterized in that step (2) prepares the hydrophobicity titanium dioxide containing sulfite ion
Silicon nano the preparation method is as follows: the hydrophobic silica nanoparticle of sulfhydrylation of step (1) preparation is immersed in
In hydrogen peroxide, every liter of hydrogen peroxide contains the hydrophobic silica nanoparticle 10-100g of sulfhydrylation, and 2-24h is stirred at room temperature, from
The heart, washing, drying, obtain the hydrophobic silica nanoparticle containing sulfite ion, which contains
Sulfite ion and long alkyl chains are C3-C16Hydrophobic alkyl chain.
6. the method as described in claim 1, it is characterized in that step (3) prepare hydrophobic solid acid the preparation method is as follows: will
Hydrophobic silica nanoparticle containing sulfite ion made from step (2) is dispersed in the dilute sulfuric acid of 0.1-1mol/L
In solution, the content in every liter of dilution heat of sulfuric acid of the hydrophobic silica nanoparticle containing sulfite ion is 10-
2-24h is stirred at room temperature in 100g, and centrifugation, washing, drying obtain hydrophobic solid acid, which is rich in sulfonic group and alkane
Base chain length is C3-C16Hydrophobic alkyl chain.
7. the method as described in claim 1, it is characterized in that hydrophobic solid acid catalysis fructose prepares the system of 5 hydroxymethyl furfural
Preparation Method is as follows: hydrophobic solid acid made from fructose, step (3) is distributed to the H that volume ratio is 0.1:1-20:12O/ diformazan
In base sulfoxide mixed solution, the content of fructose and hydrophobic solid acid in every liter of mixed solution be respectively 0.1-50mol and
0.5-50g, and it is stirred to react 0.5-12h under 80-150 DEG C, 100-500rpm revolving speed, obtain product 5 hydroxymethyl furfural.
Priority Applications (1)
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