CN106279077B - A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural - Google Patents
A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural Download PDFInfo
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- hydroxymethyl furfural
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- phosphotungstate
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000005715 Fructose Substances 0.000 claims abstract description 14
- 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 abstract description 14
- 229930091371 Fructose Natural products 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 15
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 13
- 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 8
- 239000002253 acid Substances 0.000 description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001299 aldehydes Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural, using composite mixed phosphotungstate as catalyst, synthesize 5 hydroxymethyl furfural by fructose dehydration in n,N-Dimethylformamide solvent.The structural formula for the composite mixed phosphotungstate that the present invention uses are as follows:, wherein R=- C16H33Or-C18H37, x=0.25 ~ 1.0, y=0.25 ~ 1.0.The advantage of the invention is that the catalytic activity of related composite mixed phosphotungstate is high, selectivity is good, to realize efficiently synthesizing for 5 hydroxymethyl furfural, and catalyst preparation process is simple, it is easily isolated, it is reusable.
Description
Technical field
The present invention relates to a kind of method for synthesizing 5 hydroxymethyl furfural, in particular to a kind of composite mixed phosphotungstate catalysis
The method for synthesizing 5 hydroxymethyl furfural.
Background technique
The used energy is mainly derived from the non-renewable resources such as petroleum, coal and natural gas in the world at present, with change
The sustainable resource focus of interest as our times is developed in the increasingly reduction of stone resource.Biomass is a kind of sustainability
Resource, enormous amount is cheap, biodegradable, and constantly regenerating.5 hydroxymethyl furfural is as a kind of novel life
Substance based platform compound, it and it disubstituted derivatives can be used as one of excellent substitute of oil fuel, list
Body can synthesize the high molecular material with the characteristics such as optical activity, biodegradable, and because its furan nucleus with high activity,
Aromatic alcohol, fragrant aldehyde structure can be used to prepare insecticide, pesticide, fungicide, perfume, fragrance etc..
It is considered most with prospects by the process route that fructose dehydration prepares 5 hydroxymethyl furfural, core key technology
One of be the exploitation of effective catalyst.Although the liquid acid catalysts such as sulfuric acid, which prepare 5 hydroxymethyl furfural to fructose dehydration, to be had
Higher catalytic activity, but the by-product reacted is more, and the separating energy consumption of product is high, sulfuric acid severe corrosion to equipment, and generates
A large amount of acid-bearing wastewaters cause serious environmental pollution.Therefore, in recent years, preparation 5- methylol chaff is dehydrated about fructose both at home and abroad
The exploitation of the catalyst of aldehyde focuses primarily upon solid acid.Heteropoly acid and its esters have acid strong, surface acidity center density height
And the advantages such as easily prepared, it is that one kind obtains the heavy duty detergent solid acid catalyst of extensive concern.Bent scape equality heteropoly acid or miscellaneous
Multi-acid salt catalysis fructose prepares 5 hydroxymethyl furfural, but yield is less than 72%(song scape equality, CN 101289435A)；Qu Yongshui etc.
Influence of the different phosphotungstates to fructose hydrolysis effect is had studied, and is found with CePW12O40For catalyst, fructose is at 160 DEG C
8 h of lower reaction, the molar yield of 5 hydroxymethyl furfural are more than 90%(song water etc. forever, Beijing University of Chemical Technology's journal, 2012,39 (4):
12-16)；Xu Jie etc. prepares 5 hydroxymethyl furfural using the catalysis fructose dehydration of titanium dioxide silicon substrate hydrophobic nano solid-acid material,
Yield is up to 85%(Xu Jie etc., CN 103788033A).
Prior art still has that reaction temperature is high, the reaction time is long, product yield is low, the reuse of catalyst
The defects of property is poor.Therefore, the exploitation good solid acid catalyst of efficient, stable, easily separated and repeat performance is still this
The technical staff in field technical problem in the urgent need to address.
Summary of the invention
The purpose of the present invention is to provide a kind of efficient, low energy consumption, the side of environment amenable synthesis 5 hydroxymethyl furfural
Method.
The present invention provides a kind of methods that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural: with composite mixed
Phosphotungstate is catalyst, synthesizes 5 hydroxymethyl furfural by fructose dehydration in n,N-Dimethylformamide solvent, described compound
Adulterate the structural formula of phosphotungstate are as follows:
Wherein, R=- C16H33Or-C18H37, x=0.25 ~ 1.0, y=0.25 ~ 1.0.
Further, the preparation method of the composite mixed phosphotungstate: the cetyl of 0.25~1.0 mmol is weighed
Trimethyl ammonium chloride or the phosphotungstic acid of octadecyltrimethylammonium chloride, the cesium carbonate of 0.25~1.0 mmol and 1 mmol difference
It is dissolved in 20 ml deionized waters；After being completely dissolved, under conditions of room temperature and lasting stirring, first by cetyl trimethyl
Ammonium chloride or octadecyltrimethylammonium chloride solution are slowly added dropwise into Salkowski's solution, are further continued for cesium carbonate is slowly added dropwise molten
Liquid increasingly generates white precipitate；After dripping, continue to stir 0.5 h, then still aging 1 h.White precipitate is separated by filtration
Afterwards, dry, the composite mixed phosphotungstate of quaternary ammonium, caesium can be obtained.
Further, the mass ratio of the composite mixed phosphotungstate and fructose is 3~15:100.
Further, the reaction temperature of the synthesis 5 hydroxymethyl furfural is 100 ~ 140 DEG C.
Further, the reaction time of the synthesis 5 hydroxymethyl furfural is 20~120 minutes.
Technical solution according to the present invention has the advantage that (1) quaternary ammonium, the composite mixed phosphotungstate of caesium have both
The acid site Lewis and proton acid site, and there is highly acid, high surface area, highdensity surface acid center, make it to catalysis fruit
Sugared dehydration prepares 5 hydroxymethyl furfural with excellent catalytic activity；(2) the composite mixed phosphotungstate of quaternary ammonium, caesium has super-hydrophobic
Property, the compatibility of product 5 hydroxymethyl furfural and catalyst is poor, can effectively avoid 5 hydroxymethyl furfural and continues to react, and makes to produce
The selectivity of object 5 hydroxymethyl furfural is higher；(3) catalyst preparation process is simple, without processing can direct reuse with react
The separation of system is simple, and low energy consumption, is convenient for industrialized production.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below.For those of skill in the art
For member, from detailed description of the invention, above and other objects, features and advantages of the invention be will be evident.
Embodiment 1:
The preparation of catalyst: 0.5 mmol hexadecyltrimethylammonium chloride, 0.5 mmol cesium carbonate and 1 mmol are weighed
Phosphotungstic acid is dissolved in respectively in 20 ml deionized waters；After being completely dissolved, under conditions of room temperature and lasting stirring, first by 16
Alkyl trimethyl ammonium chloride solution is slowly added dropwise into Salkowski's solution, is further continued for that cesium carbonate solution is slowly added dropwise, increasingly generates
White precipitate；After dripping, continue to stir 0.5 h, then still aging 1 h.It is dry after white precipitate is separated by filtration, i.e.,
It is [(C that molecular formula, which can be obtained,16H33)N(CH3)3]0.5Cs0.5H2PW12O40Composite mixed phosphotungstate.
Embodiment 2:
The preparation of catalyst: the additional amount of cesium carbonate is only changed to 1 mmol with embodiment 1 by preparation process, can be divided
Minor is [(C16H33)N(CH3)3]0.5Cs1H1.5PW12O40Composite mixed phosphotungstate.
Embodiment 3:
The preparation of catalyst: the additional amount of cesium carbonate is only changed to 0.25 mmol with embodiment 1 by preparation process, can be obtained
Molecular formula is [(C16H33)N(CH3)3]0.5Cs0.25H2.25PW12O40Composite mixed phosphotungstate.
Embodiment 4:
The preparation of catalyst: the additional amount of hexadecyltrimethylammonium chloride is only changed to 1 with embodiment 1 by preparation process
Mmol, it is [(C that molecular formula, which can be obtained,16H33)N(CH3)3]1Cs0.5H1.5PW12O40Composite mixed phosphotungstate.
Embodiment 5:
The preparation of catalyst: the additional amount of hexadecyltrimethylammonium chloride is only changed to by preparation process with embodiment 1
0.25 mmol, it is [(C that molecular formula, which can be obtained,16H33)N(CH3)3]0.25Cs0.5H2.25PW12O40Composite mixed phosphotungstate.
Embodiment 6:
The preparation of catalyst: hexadecyltrimethylammonium chloride is only replaced with octadecyl with embodiment 1 by preparation process
Trimethyl ammonium chloride, it is [(C that molecular formula, which can be obtained,18H37)N(CH3)3]0.5Cs0.5H2PW12O40Composite mixed phosphotungstate.
Embodiment 7:
1 g fructose, 20 g N,N-dimethylformamides are added in the reactor for being equipped with thermometer and reflux condensing tube
With the [(C prepared in 0.1 g embodiment 116H33)N(CH3)3]0.5Cs0.5H2PW12O40Catalyst opens stirring, is warming up to 120
DEG C, it reacts 60 minutes.After reaction system is cooled to room temperature, centrifuge separation, filtrate uses liquid chromatographic detection, and product yield is shown in Table
1。
Embodiment 8:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 2
[(C16H33)N(CH3)3]0.5Cs1H1.5PW12O40, product yield is shown in Table 1.
Embodiment 9:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 3
[(C16H33)N(CH3)3]0.5Cs0.25H2.25PW12O40, product yield is shown in Table 1.
Embodiment 10:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 4
[(C16H33)N(CH3)3]1Cs0.5H1.5PW12O40, product yield is shown in Table 1.
Embodiment 11:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 5
[(C16H33)N(CH3)3]0.25Cs0.5H2.25PW12O40, product yield is shown in Table 1.
Embodiment 12:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 6
[(C18H37)N(CH3)3]0.5Cs0.5H2PW12O40, product yield is shown in Table 1.
Embodiment 13:
Using reaction condition and detection method same as Example 7, the dosage of catalyst is only changed to 0.03g, product
Yield is shown in Table 1.
Embodiment 14:
Using reaction condition and detection method same as Example 7, the dosage of catalyst is only changed to 0.15g, product
Yield is shown in Table 1.
Embodiment 15:
Using reaction condition and detection method same as Example 7, reaction temperature is only changed to 100 DEG C, product yield
It is shown in Table 1.
Embodiment 16:
Using reaction condition and detection method same as Example 7, reaction temperature is only changed to 140 DEG C, product yield
It is shown in Table 1.
Embodiment 17:
Using reaction condition and detection method same as Example 7, will only be changed in the reaction time 20 minutes, product yield
It is shown in Table 1.
Embodiment 18:
It using reaction condition and detection method same as Example 7, will only be changed in the reaction time 120 minutes, product is received
Rate is shown in Table 1.
Embodiment 19:
Circulation by catalyst used in embodiment 7, without any processing after centrifuge separation, for next batch
Reaction, the reaction condition and detection method of circular response are same as Example 7, and after being recycled 10 times, product yield is shown in Table 1.
Comparative example 1:
Using reaction condition and detection method same as Example 7, catalyst is only changed to [(C16H33)N(CH3)3]1H2PW12O40, product yield is shown in Table 1.
Comparative example 2:
Using reaction condition and detection method same as Example 7, catalyst is only changed to Cs1H2PW12O40, product receipts
Rate is shown in Table 1.
Table 1: the product yield of embodiment and comparative example.
According to the result of table 1, the composite mixed phosphotungstate of quaternary ammonium of the present invention, caesium is dehydrated synthesis 5- hydroxyl first to fructose
The reaction of base furfural has very excellent catalytic performance, and catalytic activity is better than traditional single type ion doping phosphotungstic acid
There is not the phenomenon that activity is decreased obviously after 10 times are reused in salt, catalyst.In addition, catalyst is easily isolated, in temperature
Higher product yield is obtained under conditions of.
It should be appreciated that although the present invention has carried out clear explanation by above embodiments, without departing substantially from the present invention
Spirit and its essence in the case where, person of ordinary skill in the field make in accordance with the present invention it is various it is corresponding variation and
Amendment, but these corresponding variations and modifications all should belong to scope of protection of the claims of the invention.
Claims (4)
1. a kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural, which is characterized in that with composite mixed phosphorus
Tungstates is catalyst, synthesizes 5 hydroxymethyl furfural by fructose dehydration in n,N-Dimethylformamide solvent, described compound to mix
The structural formula of miscellaneous phosphotungstate are as follows:
Wherein, R=- C16H33Or-C18H37, x=0.25 ~ 1.0, y=0.25 ~ 1.0.
2. the method according to claim 1 for catalyzing and synthesizing 5 hydroxymethyl furfural, which is characterized in that the composite mixed phosphorus
The mass ratio of tungstates and fructose is 3~15:100.
3. the method according to claim 1 for catalyzing and synthesizing 5 hydroxymethyl furfural, which is characterized in that the reaction temperature
It is 100~140 DEG C.
4. the method according to claim 1 for catalyzing and synthesizing 5 hydroxymethyl furfural, which is characterized in that the reaction time is
20~120 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610596930.7A CN106279077B (en) | 2016-07-27 | 2016-07-27 | A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610596930.7A CN106279077B (en) | 2016-07-27 | 2016-07-27 | A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106279077A CN106279077A (en) | 2017-01-04 |
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| CN101289435A (en) * | 2008-06-05 | 2008-10-22 | 大连理工大学 | Process for preparing 5-hydroxymethyl-furfural |
| CN105377825A (en) * | 2013-05-09 | 2016-03-02 | 诺瓦蒙特股份公司 | Process for the synthesis of 5-hydroxymethylfurfural from saccharides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101289435A (en) * | 2008-06-05 | 2008-10-22 | 大连理工大学 | Process for preparing 5-hydroxymethyl-furfural |
| CN105377825A (en) * | 2013-05-09 | 2016-03-02 | 诺瓦蒙特股份公司 | Process for the synthesis of 5-hydroxymethylfurfural from saccharides |
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| Acidic characterization and activity of (NH4)xCs2.5-xH0.5PW12O40 catalysts in the esterification reaction of oleic acid with ethanol;Joicy S. Santos et al.;《Applied Catalysis A: General》;20120721;第443-444卷;33-39 |
| Chiral Amine–Polyoxometalate Hybrids as Recoverable Asymmetric Enamine Catalysts under Neat and Aqueous Conditions;Jiuyuan Li et al.;《Eur. J. Org. Chem.》;20091231;132-140 |
| Star-shaped Keggin-type heteropolytungstate nanostructure as a new catalyst for the preparation of quinoxaline derivatives;Majid Masteri-Farahani et al.;《C. R. Chimie》;20140916;第17卷;1136-1143 |
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Application publication date: 20170104 Assignee: Hunan Xingxun New Materials Co.,Ltd. Assignor: SHAOYANG University Contract record no.: X2023980047874 Denomination of invention: A method for catalytic synthesis of 5-hydroxymethylfurfural using composite doped phosphotungstate Granted publication date: 20190104 License type: Common License Record date: 20231124 |
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