CN106279077A - A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 Hydroxymethylfurfural - Google Patents
A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 Hydroxymethylfurfural Download PDFInfo
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- CN106279077A CN106279077A CN201610596930.7A CN201610596930A CN106279077A CN 106279077 A CN106279077 A CN 106279077A CN 201610596930 A CN201610596930 A CN 201610596930A CN 106279077 A CN106279077 A CN 106279077A
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- Prior art keywords
- composite mixed
- catalyst
- hydroxymethyl furfural
- phosphotungstate
- hydroxymethylfurfural
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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
- 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 15
- 229930091371 Fructose Natural products 0.000 claims abstract description 15
- 239000005715 Fructose Substances 0.000 claims abstract description 14
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 230000004044 response Effects 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 21
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 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 abstract description 4
- 239000000047 product Substances 0.000 description 21
- 238000001514 detection method Methods 0.000 description 15
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 13
- 229960002737 fructose Drugs 0.000 description 12
- 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 10
- 230000008859 change Effects 0.000 description 8
- 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
- 239000002253 acid Substances 0.000 description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- -1 antibacterial Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000008569 process Effects 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 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 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
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000003934 aromatic aldehydes Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel 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
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance 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
Landscapes
- 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 method that composite mixed phosphotungstate catalyzes and synthesizes 5 Hydroxymethylfurfural, with composite mixed phosphotungstate as catalyst, by fructose dehydration synthesis 5 Hydroxymethylfurfural in N, N solvent dimethylformamide.The structural formula of the composite mixed phosphotungstate that the present invention uses is:, wherein, R=C16H33Or C18H37, x=0.25 ~ 1.0, y=0.25 ~ 1.0.It is an advantage of the current invention that the catalysis activity height of involved composite mixed phosphotungstate, selectivity are good, thus realize efficiently synthesizing of 5 Hydroxymethylfurfural, and catalyst preparation process is simple, it is easy to separate, reusable.
Description
Technical field
The present invention relates to a kind of method synthesizing 5 hydroxymethyl furfural, be catalyzed particularly to a kind of composite mixed phosphotungstate
The method of synthesis 5 hydroxymethyl furfural.
Background technology
The energy used in the world at present is mainly derived from the non-renewable resources such as oil, coal and natural gas, along with change
The minimizing day by day of stone resource, developing sustainable resource becomes our times institute focus of attention.Biomass are a kind of sustainabilities
Resource, enormous amount, cheap, biodegradable and constantly regenerating.5 hydroxymethyl furfural is as a kind of novel life
Material based platform compound, it and it disubstituted derivatives can be as one of excellent substitute of oil fuel, and it is single
Body can synthesize and has optical activity, the macromolecular material of the characteristic such as biodegradable, and because of its have highly active furan nucleus,
Aromatic alcohol, aromatic aldehyde structure, can be used to prepare insecticide, pesticide, antibacterial, perfume, spice etc..
The process route being prepared 5 hydroxymethyl furfural by fructose dehydration is considered most with prospects, its core key technology
One of be the exploitation of effective catalyst.Have although fructose dehydration is prepared 5 hydroxymethyl furfural by the liquid acid catalysts such as sulphuric acid
Higher catalysis activity, but the by-product of reaction is more, and the separating energy consumption of product is high, and sulphuric acid is serious to equipment corrosion, and produces
A large amount of acid-bearing wastewaters, cause serious environmental pollution.Therefore, in recent years, both at home and abroad about fructose dehydration preparation 5-methylol bran
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 advantage such as easily prepared, it is the class heavy duty detergent solid acid catalyst that obtains 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.
Have studied the impact on fructose hydrolysis effect of the different phosphotungstates, and find with CePW12O40For catalyst, fructose is at 160 DEG C
Lower reaction 8 h, the molar yield of 5 hydroxymethyl furfural more than 90%(song water forever etc., Beijing University of Chemical Technology's journal, 2012,39 (4):
12-16)；Xu Jie etc. use the catalysis fructose dehydration of silicon-dioxide-substrate hydrophobic nano solid-acid material to prepare 5 hydroxymethyl furfural,
Productivity is up to 85%(Xu Jie etc., CN 103788033A).
Prior art yet suffers from that reaction temperature height, response time length, product yield be low, the reusing of catalyst
Property difference etc. defect.Therefore, develop efficient, stable, easily separated and that repeat performance is good solid acid catalyst and remain this
The technical problem that the technical staff in field is in the urgent need to address.
Summary of the invention
It is an object of the invention to provide a kind of efficiently, low energy consumption, the side of environment amenable synthesis 5 hydroxymethyl furfural
Method.
The invention provides a kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural: with composite mixed
Phosphotungstate is catalyst, by fructose dehydration synthesis 5 hydroxymethyl furfural in DMF solvent, described compound
The structural formula of Doping Phosphorus tungstates is:
Wherein, R=-C16H33Or-C18H37, x=0.25 ~ 1.0, y=0.25 ~ 1.0.
Further, the preparation method of described composite mixed phosphotungstate: weigh the cetyl of 0.25～1.0 mmol
Trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride, 0.25～1.0 mmol cesium carbonate and 1 mmol phosphotungstic acid respectively
It is dissolved in 20 ml deionized waters；After being completely dissolved, room temperature and continuously stirred under conditions of, first by cetyl trimethyl
Ammonium chloride or octadecyl trimethyl ammonium chloride solution are slowly added dropwise to Salkowski's solution, are further continued for being slowly added dropwise cesium carbonate molten
Liquid, increasingly generates white precipitate；After dripping, continue stirring 0.5 h, more still aging 1 h.White precipitate is separated by filtration
After, it is dried, i.e. can get quaternary ammonium, the composite mixed phosphotungstate of caesium.
Further, described composite mixed phosphotungstate is 3～15:100 with the mass ratio of fructose.
Further, the reaction temperature of described synthesis 5 hydroxymethyl furfural is 100 ~ 140 DEG C.
Further, the response time of described synthesis 5 hydroxymethyl furfural is 20～120 minutes.
Technical scheme involved in the present invention has the advantage that (1) quaternary ammonium, the composite mixed phosphotungstate of caesium have concurrently
Lewis acid site and Bronsted acid center, and there is highly acid, high surface, highdensity surface acid center so that it is to catalysis fruit
Sugar dehydration is prepared 5 hydroxymethyl furfural and is had the catalysis activity of excellence；(2) quaternary ammonium, the composite mixed phosphotungstate of caesium have super-hydrophobic
Property, product 5 hydroxymethyl furfural is poor with the affinity of catalyst, and can be prevented effectively from 5 hydroxymethyl furfural continues to react, and makes product
The selectivity of thing 5 hydroxymethyl furfural is higher；(3) catalyst preparation process is simple, it is not necessary to processing can direct reuse and reaction
The separation of system is simple, and energy consumption is low, it is simple to industrialized production.
Detailed description of the invention
Below the detailed description of the invention of the present invention is described in further detail.For those of skill in the art
For Yuan, from detailed description of the invention, the above and other objects, features and advantages of the present invention will be apparent to.
Embodiment 1:
The preparation of catalyst: weigh 0.5 mmol hexadecyltrimethylammonium chloride, 0.5 mmol cesium carbonate and 1 mmol phosphorus tungsten
Acid is dissolved in 20 ml deionized waters respectively；After being completely dissolved, room temperature and continuously stirred under conditions of, first by cetyl
Trimethyl ammonia chloride ammonium salt solution is slowly added dropwise to Salkowski's solution, is further continued for being slowly added dropwise cesium carbonate solution, increasingly generates white
Precipitation；After dripping, continue stirring 0.5 h, more still aging 1 h.After white precipitate is separated by filtration, it is dried,
It is [(C to molecular formula16H33)N(CH3)3]0.5Cs0.5H2PW12O40Composite mixed phosphotungstate.
Embodiment 2:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of cesium carbonate into 1 mmol, available molecular formula
For [(C16H33)N(CH3)3]0.5Cs1H1.5PW12O40Composite mixed phosphotungstate.
Embodiment 3:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of cesium carbonate into 0.25 mmol, available molecule
Formula is [(C16H33)N(CH3)3]0.5Cs0.25H2.25PW12O40Composite mixed phosphotungstate.
Embodiment 4:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of hexadecyltrimethylammonium chloride into 1
Mmol, available molecular formula is [(C16H33)N(CH3)3]1Cs0.5H1.5PW12O40Composite mixed phosphotungstate.
Embodiment 5:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of hexadecyltrimethylammonium chloride into 0.25
Mmol, available molecular formula is [(C16H33)N(CH3)3]0.25Cs0.5H2.25PW12O40Composite mixed phosphotungstate.
Embodiment 6:
The preparation of catalyst: hexadecyltrimethylammonium chloride, with embodiment 1, is only replaced with octadecyl front three by preparation process
Ammonium chloride, available molecular formula is [(C18H37)N(CH3)3]0.5Cs0.5H2PW12O40Composite mixed phosphotungstate.
Embodiment 7:
Add in being equipped with the reactor of thermometer and reflux condensing tube 1 g fructose, 20 g N,N-dimethylformamides and
[(the C of preparation in 0.1 g embodiment 116H33)N(CH3)3]0.5Cs0.5H2PW12O40Catalyst, opens stirring, is warming up to 120 DEG C,
React 60 minutes.After reaction system is cooled to room temperature, centrifugation, filtrate uses liquid chromatographic detection, and product yield is shown in Table 1.
Embodiment 8:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 2
[(C16H33)N(CH3)3]0.5Cs1H1.5PW12O40, product yield is shown in Table 1.
Embodiment 9:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 3
[(C16H33)N(CH3)3]0.5Cs0.25H2.25PW12O40, product yield is shown in Table 1.
Embodiment 10:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 4
[(C16H33)N(CH3)3]1Cs0.5H1.5PW12O40, product yield is shown in Table 1.
Embodiment 11:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 5
[(C16H33)N(CH3)3]0.25Cs0.5H2.25PW12O40, product yield is shown in Table 1.
Embodiment 12:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 6
[(C18H37)N(CH3)3]0.5Cs0.5H2PW12O40, product yield is shown in Table 1.
Embodiment 13:
Use reaction condition same as in Example 7 and detection method, only change the consumption of catalyst into 0.03g, product yield
It is shown in Table 1.
Embodiment 14:
Use reaction condition same as in Example 7 and detection method, only change the consumption of catalyst into 0.15g, product yield
It is shown in Table 1.
Embodiment 15:
Using reaction condition same as in Example 7 and detection method, only reaction temperature changes 100 DEG C into, product yield is shown in Table
1。
Embodiment 16:
Using reaction condition same as in Example 7 and detection method, only reaction temperature changes 140 DEG C into, product yield is shown in Table
1。
Embodiment 17:
Using reaction condition same as in Example 7 and detection method, only will change in the response time 20 minutes, product yield is shown in Table
1。
Embodiment 18:
Using reaction condition same as in Example 7 and detection method, only will change in the response time 120 minutes, product yield is shown in
Table 1.
Embodiment 19:
Catalyst after using in embodiment 7, without any process after centrifugation, anti-for the circulation of next batch
Should, the reaction condition of circular response is same as in Example 7 with detection method, and after recycling 10 times, product yield is shown in Table 1.
Comparative example 1:
Use reaction condition same as in Example 7 and detection method, only change catalyst into [(C16H33)N(CH3)3]1H2PW12O40, product yield is shown in Table 1.
Comparative example 2:
Use reaction condition same as in Example 7 and detection method, only change catalyst into Cs1H2PW12O40, product yield is shown in
Table 1.
Table 1: embodiment and the product yield of comparative example.
According to the result of table 1, the composite mixed phosphotungstate of the quaternary ammonium that the present invention relates to, caesium is to fructose dehydration synthesis 5-hydroxyl first
The reaction of base furfural has the most excellent catalytic performance, and its catalysis activity is better than traditional unitary type ion doping phosphotungstic acid
Salt, there is not, after 10 times are reused, the phenomenon that activity is decreased obviously in catalyst.Additionally, catalyst is easily isolated, in temperature
Higher product yield is obtained under conditions of with.
Although should be appreciated that the present invention has carried out understanding explanation by above example, but without departing substantially from the present invention
Spirit and essence in the case of, person of ordinary skill in the field when can according to the present invention make various corresponding change and
Revise, but these corresponding variations and modifications all should belong to the scope of the claims of the present invention.
Claims (4)
1. the method that a composite mixed phosphotungstate catalyzes and synthesizes 5 hydroxymethyl furfural, it is characterised in that with composite mixed phosphorus
Tungstates is catalyst, and by fructose dehydration synthesis 5 hydroxymethyl furfural in DMF solvent, described being combined is mixed
The structural formula of miscellaneous phosphotungstate is:
Wherein, R=-C16H33Or-C18H37, x=0.25 ~ 1.0, y=0.25 ~ 1.0.
The method catalyzing and synthesizing 5 hydroxymethyl furfural the most according to claim 1, it is characterised in that described composite mixed phosphorus
Tungstates is 3～15:100 with the mass ratio of fructose.
The method catalyzing and synthesizing 5 hydroxymethyl furfural the most according to claim 1, it is characterised in that described reaction temperature
It it is 100～140 DEG C.
The method catalyzing and synthesizing 5 hydroxymethyl furfural the most according to claim 1, it is characterised in that the described response 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 |
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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 |
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| Publication Number | Publication Date |
|---|---|
| CN106279077A true CN106279077A (en) | 2017-01-04 |
| CN106279077B CN106279077B (en) | 2019-01-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084120A (en) * | 2017-12-29 | 2018-05-29 | 山东理工大学 | It is used to prepare difunctional solid catalyst of soda acid of 5 hydroxymethyl furfural and its preparation method and application |
| CN108997275A (en) * | 2018-06-20 | 2018-12-14 | 昆明理工大学 | A method of primary product distribution in control fructose-ethanol synthesis system |
| CN114426528A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Method for continuously preparing 5-hydroxymethylfurfural |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-07-27 CN CN201610596930.7A patent/CN106279077B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| JIUYUAN LI ET AL.: "Chiral Amine–Polyoxometalate Hybrids as Recoverable Asymmetric Enamine Catalysts under Neat and Aqueous Conditions", 《EUR. J. ORG. CHEM.》 * |
| JOICY S. SANTOS ET AL.: "Acidic characterization and activity of (NH4)xCs2.5-xH0.5PW12O40 catalysts in the esterification reaction of oleic acid with ethanol", 《APPLIED CATALYSIS A: GENERAL》 * |
| MAJID MASTERI-FARAHANI ET AL.: "Star-shaped Keggin-type heteropolytungstate nanostructure as a new catalyst for the preparation of quinoxaline derivatives", 《C. R. CHIMIE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084120A (en) * | 2017-12-29 | 2018-05-29 | 山东理工大学 | It is used to prepare difunctional solid catalyst of soda acid of 5 hydroxymethyl furfural and its preparation method and application |
| CN108084120B (en) * | 2017-12-29 | 2019-07-05 | 山东理工大学 | It is used to prepare the difunctional solid catalyst of soda acid and its preparation method and application of 5 hydroxymethyl furfural |
| CN108997275A (en) * | 2018-06-20 | 2018-12-14 | 昆明理工大学 | A method of primary product distribution in control fructose-ethanol synthesis system |
| CN114426528A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Method for continuously preparing 5-hydroxymethylfurfural |
| CN114426528B (en) * | 2020-09-25 | 2024-02-09 | 中国石油化工股份有限公司 | Method for continuously preparing 5-hydroxymethylfurfural |
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| CN106279077B (en) | 2019-01-04 |
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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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