CN108187744A - A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal - Google Patents
A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal Download PDFInfo
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- CN108187744A CN108187744A CN201810080135.1A CN201810080135A CN108187744A CN 108187744 A CN108187744 A CN 108187744A CN 201810080135 A CN201810080135 A CN 201810080135A CN 108187744 A CN108187744 A CN 108187744A
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- furfural
- aluminium
- phosphotungstic acid
- glycol acetal
- salt
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- -1 aluminium phosphotungstic acid ammonium compound salt Chemical class 0.000 title claims abstract description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004411 aluminium Substances 0.000 title claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000006482 condensation reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 description 10
- 239000011964 heteropoly acid Substances 0.000 description 7
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002786 root growth Effects 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of methods that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal, using aluminium phosphotungstic acid ammonium compound salt as catalyst, condensation reaction generation furfural glycol acetal is occurred by furfural and ethylene glycol, the skeleton symbol of the aluminium phosphotungstic acid ammonium compound salt is：(NH4)xAlyH(3‑x‑3y)PW12O40, wherein, x=0.4 ~ 0.6, y=0.6 ~ 0.8.The specific surface area and surface acid density of aluminium phosphotungstic acid ammonium compound salt catalyst of the present invention are higher, and with suitable acid strength, make its catalytic performance excellent, product yield high.In addition, raw material is easy to get needed for catalyst, preparation process is simple, and catalyst and product are easily separated, reusable.
Description
Technical field
The present invention relates to a kind of synthetic method of furfural glycol acetal, more particularly to a kind of aluminium phosphotungstic acid ammonium compound salt is urged
The method of furfural glycol acetal is combined to, belongs to organic synthesis field.
Background technology
Furfural glycol acetal is a kind of important chemical intermediate raw material, while is obtained extensively in flavorant, fragrance
General application.In addition, it or a kind of novel low-toxicity plant growth regulator, can promote the root growth of plant, enhance plant
Drought resisting and saline-alkaline tolerance.
In the traditional processing technology of furfural glycol acetal, mainly use the liquid acids such as the concentrated sulfuric acid, hydrochloric acid and phosphoric acid for
Catalyst, catalyst it is cheap, and catalytic activity is higher.However, the by-product of reaction is more, and the separating-purifying of product
It is difficult.In addition, the liquid acids severe corrosion to equipment such as sulfuric acid, and a large amount of acid-bearing wastewaters are generated, cause serious environmental pollution.For
Overcome disadvantages described above, both at home and abroad develop it is a series of for synthesizing the heterogeneous catalysts of furfural glycol acetal, as super acids,
Acid-exchange resin, heteropoly acid and loaded catalyst etc..Wherein, heteropoly acid has green non-poisonous, activity and selectivity
The features such as high, but there is also be easy to run off, specific surface area is low and thermal stability is poor the problems such as.Solution to the problems described above be by
Loaded by heteropoly acid on porous support or is changed into insoluble heteropoly acid saline catalyst.Compared with carried heteropoly acid,
Heteropoly acid saline catalyst is easily prepared, and surface acid strength is easy to regulate and control with acid amount, is widely used in synthesizing the reaction of acetal
In.Such as silico-tungstic acid titanium salt（Yang Shuijin etc., Chemical Reaction Engineering and technique, 2003,19,9-13）, phosphotungstic acid mantoquita（Liu Qing
Deng, chemical research, 2010,21,10-14）, phosphotungstic acid aluminium salt（Liu Qing etc., Industrial Catalysis, 2010,18,50-53）, sulfonic acid work(
Ionic liquid phosphotungstate can be changed（Zhao Pingping etc., Nanjing University of Technology's journal（Natural science edition）, 2014,36,1-6）Deng
It can promote the synthesis of acetal.However, there are still activity and selective not high or repetition for above-mentioned single type heteropoly acid saline catalyst
The defects of performance is poor.
Therefore, exploitation suitable for the green, efficient, stable of industrialized production furfural glycol acetal and is easily isolated more
Phase catalyst is still the technical issues of those skilled in the art is in the urgent need to address.
Invention content
The purpose of the present invention is to provide a kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal,
This method has the advantages such as efficient, environmentally friendly and catalyst is easily separated.
A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal, using aluminium phosphotungstic acid ammonium compound salt as
By furfural and ethylene glycol condensation reaction generation furfural glycol acetal occurs for catalyst, which is characterized in that the aluminium phosphotungstic acid ammonium
The skeleton symbol of complex salt is：(NH4)xAlyH(3-x-3y)PW12O40, wherein, x=0.4 ~ 0.6, y=0.6 ~ 0.8.
Further, the preparation process of the aluminium phosphotungstic acid ammonium compound salt catalyst includes step：
（1）Aluminium salt, ammonium salt and phosphotungstic acid are mixed in solution；
（2）The isolated aluminium phosphotungstic acid ammonium compound salt after reaction.
Further, the step（1）Specially：
Aluminium salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
Further, the aluminium salt is aluminum sulfate or aluminum nitrate.
Further, the ammonium salt is ammonium carbonate or ammonium nitrate.
Further, the ratio between amount of substance of furfural and ethylene glycol is 1：1~3.
Further, the mass ratio of catalyst and furfural is 1 ~ 3：100.
Further, the temperature of condensation reaction is 90 ~ 110 DEG C.
Further, the time of condensation reaction is 1 ~ 5 hour.
Technical solution provided by the present invention has the following advantages：（1）Aluminium phosphotungstic acid ammonium compound salt of the present invention is urged
The specific surface area of agent and surface acid density are higher, and with suitable acid strength, can promote the height of furfural glycol acetal
Effect synthesis, and excessively high acid strength is avoided to lead to the increase of by-product, make its catalytic performance excellent, the high income of product；（2）It urges
Raw material is easy to get needed for agent, cheap, and preparation process is simple, high catalytic efficiency, and catalyst and product are easily separated, catalyst
It is reusable, it is suitable for scale application.
Specific embodiment
The specific embodiment of the present invention is 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 will be evident.
Embodiment 1：
The preparation of catalyst：It weighs 0.25 mmol ammonium carbonates, 0.7 mmol aluminum nitrates and 1 mmol phosphotungstic acids and is dissolved in 20 respectively
In ml deionized waters；After dissolving, under conditions of room temperature and lasting stirring, aluminum nitrate solution is slowly added dropwise to Salkowski's solution
In, it reacts 0.5 hour, then sal volatile is slowly added dropwise, increasingly generates white precipitate；After dripping, it is further continued for being stirred to react
It is 0.5 hour, still aging 1 hour, dry after precipitation is separated by filtration, you can to obtain molecular formula as (NH4)0.5Al0.7H0.4PW12O40Aluminium phosphotungstic acid ammonium compound salt.
Embodiment 2：
The preparation of catalyst：The addition of ammonium carbonate is only changed to 0.2 mmol, aluminum nitrate adds by preparation process with embodiment 1
Enter amount and be changed to 0.8 mmol, can obtain molecular formula as (NH4)0.4Al0.8H0.2PW12O40Aluminium phosphotungstic acid ammonium compound salt.
Embodiment 3：
The preparation of catalyst：The addition of ammonium carbonate is only changed to 0.3 mmol, aluminum nitrate adds by preparation process with embodiment 1
Enter amount and be changed to 0.6 mmol, can obtain molecular formula as (NH4)0.6Al0.6H0.6PW12O40Aluminium phosphotungstic acid ammonium compound salt.
Embodiment 4：
The preparation of catalyst：Ammonium carbonate is only changed to 0.25 mmol ammonium nitrate, aluminum nitrate is changed to by preparation process with embodiment 1
0.35 mmol aluminum sulfate can obtain molecular formula as (NH4)0.5Al0.7H0.4PW12O40Aluminium phosphotungstic acid ammonium compound salt.
Embodiment 5：
9.6 g furfurals are added in the reactor for being equipped with thermometer, agitating device, condenser pipe and division box（0.1 mol）、
7.5 g ethylene glycol（0.12 mol）With (the NH prepared in 0.145 g embodiments 14)0.5Al0.7H0.4PW12O40Catalyst is opened
Stirring, is warming up to 100 DEG C, starts timing when starting to occur backflow phenomenon in condenser pipe, reacts 2 h.Reaction system is cooled to
It after room temperature, is separated by filtration, filtrate is quantitatively detected using gas-chromatography, and the yield of furfural glycol acetal is 95.5%.
Embodiment 6：
Using reaction condition and detection method same as Example 5, catalyst is only changed to what is prepared in embodiment 2
(NH4)0.4Al0.8H0.2PW12O40, the yield of furfural glycol acetal is 90.6%.
Embodiment 7：
Using reaction condition and detection method same as Example 5, catalyst is only changed to what is prepared in embodiment 3
(NH4)0.6Al0.6H0.6PW12O40, the yield of furfural glycol acetal is 93.7%.
Embodiment 8：
Using reaction condition and detection method same as Example 5, catalyst is only changed to what is prepared in embodiment 4
(NH4)0.5Al0.7H0.4PW12O40, the yield of furfural glycol acetal is 95.3%.
Embodiment 9：
Using reaction condition and detection method same as Example 5, the dosage of ethylene glycol is only changed to 6.2 g（0.1 mol）,
Reaction temperature is changed to 90 DEG C, and the yield of furfural glycol acetal is 83.6%.
Embodiment 10：
Using reaction condition and detection method same as Example 5, the dosage of ethylene glycol is only changed to 18.6 g（0.3
mol）, reaction temperature is changed to 110 DEG C, and the yield of furfural glycol acetal is 97.9%.
Embodiment 11：
Using reaction condition and detection method same as Example 5, the dosage of catalyst is only changed to 0.096 g, during reaction
Between be changed to 5 h, the yield of furfural glycol acetal is 97.6%.
Embodiment 12：
Using reaction condition and detection method same as Example 5, the dosage of catalyst is only changed to 0.288 g, during reaction
Between be changed to 1 h, the yield of furfural glycol acetal is 90.3%.
Embodiment 13：
It is anti-for the cycle of next batch without any processing after being separated by filtration by catalyst used in embodiment 5
Should, the reaction condition and detection method of circular response are same as Example 5, after recycling 10 times, furfural glycol acetal
Yield is 92.5%.
Comparative example 1：
Using reaction condition and detection method same as Example 5, catalyst is only changed to (NH4)2.6H0.4PW12O40, furfural
The yield of Glycol Acetal is 87.5%.
Comparative example 2：
Using reaction condition and detection method same as Example 5, catalyst is only changed to Al2.6/3H0.4PW12O40, furfural second
The yield of two acetals is 83.9%.
According to embodiment 5-13 and comparative example 1-2's as a result, aluminium phosphotungstic acid ammonium compound salt of the present invention to synthesizing chaff
The condensation reaction of aldehyde Glycol Acetal has very excellent catalytic performance, and catalytic performance is better than traditional single type phosphotungstic acid
There is not the phenomenon that activity is decreased obviously after 10 times are reused in ammonium and phosphotungstic acid aluminium salt, catalyst.In addition, catalyst system
Standby process is simple, and required raw material is easy to get, inexpensively.Therefore, technical solution of the present invention is suitable for industrial applications.
It should be appreciated that although the present invention has carried out clear explanation by above example, without departing substantially from the present invention
Spirit and its essence in the case of, person of ordinary skill in the field make in accordance with the present invention it is various it is corresponding variation and
It corrects, but these corresponding variations and modifications should all belong to the scope of the claims of the present invention.
Claims (9)
1. a kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal, using aluminium phosphotungstic acid ammonium compound salt to urge
By furfural and ethylene glycol condensation reaction generation furfural glycol acetal occurs for agent, which is characterized in that the aluminium phosphotungstic acid ammonium is answered
Close salt skeleton symbol be：(NH4)xAlyH(3-x-3y)PW12O40, wherein, x=0.4 ~ 0.6, y=0.6 ~ 0.8.
2. the method according to claim 1 for catalyzing and synthesizing furfural glycol acetal, which is characterized in that the aluminium phosphotungstic acid
The preparation process of ammonium compound salt catalyst includes step：
（1）Aluminium salt, ammonium salt and phosphotungstic acid are mixed in solution；
（2）The isolated aluminium phosphotungstic acid ammonium compound salt after reaction.
3. the method according to claim 2 for catalyzing and synthesizing furfural glycol acetal, which is characterized in that the step（1）
Specially：
Aluminium salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
4. the method according to claim 2 for catalyzing and synthesizing furfural glycol acetal, which is characterized in that the aluminium salt is sulphur
Sour aluminium or aluminum nitrate.
5. the method according to claim 2 for catalyzing and synthesizing furfural glycol acetal, which is characterized in that the ammonium salt is carbon
Sour ammonium or ammonium nitrate.
6. the method that furfural glycol acetal is catalyzed and synthesized according to claim 1-5 any one of them, which is characterized in that furfural
It is 1 with the ratio between the amount of substance of ethylene glycol：1~3.
7. the method that furfural glycol acetal is catalyzed and synthesized according to claim 1-5 any one of them, which is characterized in that catalysis
The mass ratio of agent and furfural is 1 ~ 3：100.
8. the method that furfural glycol acetal is catalyzed and synthesized according to claim 1-5 any one of them, which is characterized in that described
The temperature of condensation reaction is 90 ~ 110 DEG C.
9. the method that furfural glycol acetal is catalyzed and synthesized according to claim 1-5 any one of them, which is characterized in that described
The time of condensation reaction is 1 ~ 5 hour.
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| CN201810080135.1A CN108187744B (en) | 2018-01-27 | 2018-01-27 | Method for catalytic synthesis of furfural ethylene glycol acetal from ammonium aluminum phosphotungstate complex salt |
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| CN111517984A (en) * | 2020-06-01 | 2020-08-11 | 河北工业大学 | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
Citations (9)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111517984A (en) * | 2020-06-01 | 2020-08-11 | 河北工业大学 | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
| CN111517984B (en) * | 2020-06-01 | 2023-02-28 | 河北工业大学 | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
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