CN100577291C - Method for recovering heteropoly acid from deactivation supported type heteropoly acid catalyst - Google Patents
Method for recovering heteropoly acid from deactivation supported type heteropoly acid catalyst Download PDFInfo
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- CN100577291C CN100577291C CN200610169667A CN200610169667A CN100577291C CN 100577291 C CN100577291 C CN 100577291C CN 200610169667 A CN200610169667 A CN 200610169667A CN 200610169667 A CN200610169667 A CN 200610169667A CN 100577291 C CN100577291 C CN 100577291C
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Abstract
The invention discloses a method for recycling active constituent element heteropoly acid from inactive support heteropoly acid catalyst, which comprises the following steps that: (1) the inactive support heteropoly acid catalyst contacts with organic solvent to cause the heteropoly acid to dissolve into the organic solvent so as to get a carrier through separation, thus obtaining heteropoly acid organic solvent A; (2) organic solvent in the solution A is separated, and then remains are dissolved in water, thus obtaining heteropoly acid water solution B; (3) the water solution B is mixed with acid decontaminant to lead the heteropoly acid to carry out purification precipitation, filtration and drying of the heteropoly acid, thus obtaining heteropoly acid crystal. Compared with the prior art, the invention has simple process and does not use gases containing oxygen, oxyful as well as an ion exchange method, and the yield can reach 60 percent, thus being suitable for large scale industry; the heteropoly acid recycled has single structure and can meet the requirements of being taken as acid catalyst.
Description
Technical field
The present invention relates to a kind of method that reclaims heteropoly acid, more particularly, the present invention relates to a kind of method that from the carried heteropoly acid catalyst of inactivation, reclaims heteropoly acid.
Background technology
Heteropoly acid is the class acid that, condensation acidified by two or more inorganic oxygen-containing acid ion, dehydration obtain having cagelike structure and duct, the heteropoly acid of this class formation had both had highly acid, has oxidation-reduction quality again, therefore acid catalyst can be used as, also oxidation reduction catalyst can be used as.Heteropoly acid is loaded on the carrier equably, on silica, aluminium oxide, silica-alumina mixture or active carbon, promptly obtain carried heteropoly acid catalyst.This carried heteropoly acid catalyst can use in requiring the hydrocarbon conversion reaction of strongly acidic catalyst, as alkylated reaction, olefin hydration, formoxy-reaction, etherification reaction etc., and referring to document Chemtech, 8,432 (1978); Hydrocarbon Processing, 58 (2), 105 (1979); Chem.Lett.1177 (1983); 865 (1984); 909 (1994).Heteropoly acid has multiple structure, but in order effectively to control the activity and the selectivity of heteropolyacid catalyst, what generally use all is the heteropoly acid of single structure.Phosphotungstic acid is most widely used in heteropolyacid catalyst, and is also the most representative.In addition, also have phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid and molybdovanaphosphoric acid Mo
10V
0-3P
0.8-5X
0-3Y
0-3O
e(X is that alkali metal or alkaline-earth metal, Y are transition metal, boron, germanium, arsenic, antimony or tin; O is an oxygen, and its atomicity e depends on other atomic species, valence state and number in the structural formula) etc.
Long period uses this class carried heteropoly acid catalyst, unavoidably has the problem of catalysqt deactivation.The reason of inactivation has catalyst to be heated to cause that catalyst backbone is destroyed, catalyst surface is sticked etc. by product or accessory substance; Alkali metal on the catalyst carrier also can influence the activity of heteropoly acid.If covered byproduct of reaction on the catalyst surface, for example macromolecular organic matter, coke precursor thing can make reactive activity reduce significantly.Carried heteropoly acid catalyst behind the inactivation can't continue to use.
Various heteropoly acids all are the expensive chemical products of price, if can reclaim the active component heteropoly acid of the carried heteropoly acid catalyst of inactivation, utilize its preparation catalyst again, just can reduce the Preparation of catalysts cost greatly.In addition, the carried heteropoly acid catalyst behind the inactivation still has highly acid, if random landfill and abandoning, the heteropoly acid on the catalyst can the severe contamination underground water source.Therefore no matter, reclaim the active component heteropoly acid of the carried heteropoly acid catalyst of inactivation, be from reducing the Preparation of catalysts cost, still saying from point of view of environment protection, all significant.
The inventor finds, the heteropoly acid that loads on the single structure on the catalyst carrier has part-structure to change after catalyst carrier separates, promptly generate the heteropoly acid of multiple structure, the heteropoly acid of this multiple structure can not satisfy the requirement of preparation carried heteropoly acid catalyst.
Heteropoly acid on the carried heteropoly acid catalyst behind the recovery inactivation, heteropoly acid is more dissolved from catalyst carrier, its less important heteropoly acid and carrier and solvent of making is separated, at last, take measures to obtain the heteropoly acid of highly purified single structure, to be used for preparing carried heteropoly acid catalyst once more.
How to reclaim heteropoly acid more, improving the rate of recovery and obtaining highly purified heteropoly acid with single structure becomes a main difficult problem that reclaims heteropoly acid.
JP56163755 discloses a kind of containing at least of catalyzed alkene hydration and aldehyde gas phase oxidation a kind of load phosphomolybdic acid or the heteropolyacid catalyst renovation process of molybdovanaphosphoric acid or their salt that is applied to.Catalyst carrier is silica, aluminium oxide, diatomite or activated carbon.This method water or water and water-miscible organic solvent methyl alcohol immixture are in the carried heteropoly acid catalyst of this inactivation, the heteropoly acid that loads on the catalyst is dissolved in the solvent, after the filtration, in filtrate, feed the gas of molecule-containing keto, the catalytic activity of heteropoly acid is recovered substantially; The heteropoly acid solution that this catalytic activity is recovered substantially is adjusted to finite concentration and loads on the carrier, can make catalyst once more.This patent does not disclose the rate of recovery of heteropoly acid and the data of purity.
JP6285373 discloses a kind of containing at least of catalyzed alkene hydration and aldehyde gas phase oxidation a kind of load phosphomolybdic acid or the heteropolyacid catalyst renovation process of molybdovanaphosphoric acid and salt thereof that is applied to.Catalyst carrier is diatomite, ceramic fibre or carbon fiber.This method water or water and water-miscible organic solvent immixture are in the carried heteropoly acid catalyst of this inactivation, and the heteropoly acid that loads on the catalyst is dissolved in water or the solvent; Remove by filter insoluble carrier then, add hydrogen peroxide to solution again and become Chinese red in solution, the metaantimmonic acid that adds crystallization then in filtrate carries out ion-exchange.If will remove the impurity cationic Ca that introduces by carrier fully
2+, K
+, also need on ion exchange resin, carry out ion-exchange.Further filter then,, obtain pulverous heteropoly acid the complete evaporation drying of filtrate.This patent does not also disclose the rate of recovery of heteropoly acid and the data of purity.
Summary of the invention
The invention provides a kind of method that from the carried heteropoly acid catalyst of inactivation, reclaims the active component heteropoly acid, this method is not used oxygen-containing gas, hydrogen peroxide, do not use ion-exchange process yet, adopt the structure of the heteropoly acid crystal that simple recycling step obtains single, rate of recovery height.
Characteristics of the present invention are at first the carried heteropoly acid catalyst and the organic solvent effect of inactivation, and the heteropoly acid in the catalyst pores is dissolved in the organic solvent, isolate carrier, obtain heteropoly acid organic solution; Organic solvent in the separation solution is dissolved in residue in the water, obtains the heteropoly acid aqueous solution; Add sour scarvenger again, make heteropoly acid purifying precipitation, filtration, drying obtain the single heteropoly acid crystal of structure then.
This method that reclaims the active component heteropoly acid from the carried heteropoly acid catalyst of inactivation contains following steps:
(1), the carried heteropoly acid catalyst of inactivation is contacted with organic solvent, heteropoly acid is dissolved in the organic solvent, isolates carrier, obtain heteropoly acid organic solution A;
(2), the organic solvent among the separation solution A, residue is dissolved in the water, obtain heteropoly acid aqueous solution B;
(3), aqueous solution B is mixed with sour scarvenger, make heteropoly acid purifying precipitation, filter, drying, obtain the heteropoly acid crystal, described sour scarvenger is an inorganic acid.
By method provided by the invention, the carried heteropoly acid catalyst of described inactivation can be the carried heteropoly acid catalyst that is derived from inactivation behind the various hydrocarbon conversion reactions; Hydrocarbon conversion reaction wherein includes but not limited to alkylated reaction, olefin hydration, formoxy-reaction, etherification reaction etc.To be heteropoly acid obtain on the mixture of silica, aluminium oxide, silica-alumina or active carbon through uniform load described carried heteropoly acid catalyst, heteropoly acid wherein is the class acid that, condensation acidified by two or more inorganic oxygen-containing acid ion, dehydration obtain having cagelike structure and duct, includes but not limited to phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid of various structures etc.
In step (1), described organic solvent is any organic solvent that can dissolve heteropoly acid, is in particular the organic polar solvent that can dissolve each other with water, preferred C
1-C
3Alcohol, ketone and acid in one or more mixture, the more preferably mixture of one or more in methyl alcohol, ethanol, acetone and the acetate; The consumption of organic solvent is greater than the heteropoly acid that is contained in the carried heteropoly acid catalyst of inactivation and forms the required consumption of saturated solution in this solvent, general consumption be catalyst weight 1-10 doubly, preferred 2-5 is doubly.The temperature that catalyst contacts with organic solvent can be at the freezing point of organic solvent and the arbitrary temp between the boiling point, for accelerate dissolution, can suitably heat.The mode of contact can be leave standstill, various known or unknown modes such as stirring, boiling reflux, airtight pressurization.Time of contact can according to the way of contact with contact temperature decision, to guarantee that finally heteropoly acid is dissolved in the organic solvent fully.
In step (1), can be by the method carrier of separating such as filtering, centrifugal.
In step (2), the method of separating organic solvent can be any known or unknown method that can realize this purpose, and usual way is evaporation, and evaporation conditions can be determined according to the boiling point of organic solvent, for example water-bath evaporation, oil bath evaporation, atmospheric evaporation, reduction vaporization, or the like.The solvent that steams can be reused.
In step (2), described water is the water that does not contain or do not contain substantially other ion, can be drinking water, is preferably pure water, includes but not limited to deionized water, distilled water or electrodialytic water; The consumption of water will dissolve heteropoly acid at least fully, general consumption be heteropoly acid weight 0.4-10 doubly, preferred 2-5 is doubly.In order to improve heteropoly acid purity, can optionally the heteropoly acid aqueous solution be filtered.
In step (3), described sour scarvenger is an inorganic acid, preferred inorganic acid, more preferably hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio.Described sour scarvenger can be the aqueous solution.The consumption of acid scarvenger is wanted can make the heteropoly acid precipitation fully at least, and the concentration of sour generally speaking scarvenger in the mixed solution of aqueous solution B and sour scarvenger is with H
+Count 0.1～8.0mol/L, preferred 0.5～6.0mol/L; The purifying precipitation is not high to temperature requirement, can carry out at 0～80 ℃, and preferred temperature is 5～50 ℃; Speed and heteropoly acid solution concentration, sour scarvenger concentration and the temperature correlation of purifying precipitation were generally finished in 10 minutes～110 hours, and it is unfavorable that the time is longer than suitability for industrialized production again; The preferred sedimentation time is 1-48 hour.With sedimentation and filtration, drying, just obtain highly purified heteropoly acid crystal.
The acid scarvenger can recycle, and can further improve the yield of heteropoly acid.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
(1) removal process is not used oxygen-containing gas, hydrogen peroxide, does not use ion-exchange process yet, and flow process is simple, the yield height, and suitability for mass industrialized is used;
(2) the heteropoly acid structure of Hui Shouing is single, and the purity height can satisfy the requirement as acid catalyst.
Description of drawings
31The P-NMR nmr analysis is a kind of classical way of identifying phosphotungstic acid, phosphomolybdic acid compound purity, referring to document: J.Inorg.Chem., and 1977,16 (11): 2916; The nuclear magnetic resoance spectrum of the phosphorus atoms of different chemical environment has the characteristic peak of different chemical displacement, and the present invention adopts
31P-NMR nuclear magnetic resonance spectral method is identified the phosphotungstic acid that reclaims, the purity of phosphomolybdic acid.
Similarly,
29Si-NMR,
95The Mo-NMR nmr analysis also is a kind of classical way of identifying silico-tungstic acid, silicomolybdic acid compound purity, referring to document: J.Phys.Chem.1989,95:904; YagasakiA, Ichida H.Polyhed.1988,7:1131.The present invention adopts the method to identify the silico-tungstic acid that reclaims, the purity of silicomolybdic acid.
Fig. 1 is embodiment 1 a phosphotungstic acid sample
31The P-NMR nuclear magnetic resoance spectrum.
Fig. 2 is Comparative Examples 1 a phosphotungstic acid sample
31The P-NMR nuclear magnetic resoance spectrum.
Fig. 3 is embodiment 4 phosphomolybdic acid samples
31The P-NMR nuclear magnetic resoance spectrum.
Fig. 4 is embodiment 5 silico-tungstic acid samples
29The Si-NMR nuclear magnetic resoance spectrum.
The specific embodiment
By above direct elaboration full disclosure the present invention, the following examples will be further described specifically the present invention, but they can not be interpreted as the qualification to protection domain of the present invention.
The weight concentration of concentrated hydrochloric acid is 36%, analyzes purely, and the Beijing Chemical Plant produces; It is pure that sulfuric acid, nitric acid, methyl alcohol, ethanol, acetone, acetate are analysis, and Beijing chemical reagents corporation produces.
Embodiment 1
Take by weighing the carried heteropoly acid catalyst of 10 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is phosphotungstic acid H
3PW
12O
40, content is 25 weight %, carrier is a silicon oxide sio
2Catalyst is put into conical flask, add 20g methyl alcohol, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 15 ℃, handles 1h.Suction filtration is removed carrier, steams methyl alcohol 85 ℃ of water-baths, obtains containing the steaming excess of heteropoly acid; Add water-soluble this steaming excess of separating of 20g, adding concentration then is nitric acid 18.8 grams of 65 weight %, and the concentration that makes nitric acid in the system is with H
+Count about 5.8mol/L; It is complete to leave standstill the 48h postprecipitation under 30 ℃ of the room temperatures; Precipitation is used the Buchner funnel suction filtration, and drying obtains the white phosphotungstic acid of 1.49 grams, with H
3PW
12O
40Meter, yield is 59.6%.
The sample phosphotungstic acid
31The P-NMR nuclear magnetic resoance spectrum is seen Fig. 1.Have only the peak of a chemical shift at-14.861ppm place among Fig. 1, it is the phosphotungstic acid H with single structure
3PW
12O
40Middle phosphorus atoms
31The P-NMR nuclear magnetic resonance peak; As can be seen from Figure 1, the phosphide that does not have other structure in the sample.
Comparative Examples 1
Take by weighing the carried heteropoly acid catalyst of 10 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is phosphotungstic acid H
3PW
12O
40, content is 25 weight %, carrier is a silicon oxide sio
2Catalyst is put into conical flask, add 20g methyl alcohol, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 15 ℃, handles 1h, and suction filtration is removed carrier then, steams methyl alcohol 85 ℃ of water-baths, obtains containing the steaming excess of heteropoly acid; Add water-soluble this steaming excess of separating of 20g, with this solution as a comparison sample do
31The P-NMR nuclear magnetic resonance.
Fig. 2 is Comparative Examples 1 a phosphotungstic acid sample
31The P-NMR nuclear magnetic resoance spectrum.Be the phosphotungstic acid H of single structure at the peak at chemical shift-14.792ppm place among Fig. 2
3PW
12O
40Middle phosphorus atoms
31The P-NMR nuclear magnetic resonance peak; At the peak at chemical shift 0.360ppm place is phosphorus atoms in the phosphate radical
31The P-NMR nuclear magnetic resonance peak; Chemical shift-10.655ppm to several small peaks of-13.404ppm place appearance are heteropoly acid phosphorus atoms of other structure
31The P-NMR nuclear magnetic resonance peak.
Embodiment 2
Take by weighing the carried heteropoly acid catalyst of 50 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is a phosphotungstic acid, and content is 25wt%, and carrier is a silicon oxide sio
2Catalyst is put into conical flask, add 50g methyl alcohol, fully stir, the temperature of the hierarchy of control is 50 ℃, reflow treatment 5 hours.Suction filtration is removed carrier then, steams methyl alcohol under 85 ℃ of conditions, obtains containing the steaming excess of heteropoly acid; Add water-soluble this steaming excess of separating of 5g,, wash flask 1 time with 5g water again the solution suction filtration, must about 10ml filtrate.Adding concentration in this filtrate is sulfuric acid 0.3 gram of 96 weight %, makes the H of sulfuric acid in the system
+Proton concentration is about 0.6mol/L; Leave standstill 110h under 5 ℃, after precipitation was used the Buchner funnel suction filtration, drying obtained the white phosphotungstic acid of 6.2 grams, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 49.6%.
Embodiment 3
Take by weighing the carried heteropoly acid catalyst of 2 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is a phosphotungstic acid, and content is 25 weight %, and carrier is silica-alumina mixture, i.e. SiO
2-Al
2O
3Catalyst is put into conical flask, add 20g methyl alcohol, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 10 ℃, handles 24 hours.Suction filtration is removed carrier then, steams methyl alcohol under 85 ℃ of conditions, obtains containing the steaming excess of heteropoly acid; Add the water-soluble heteropoly acid of separating of 6g and steam excess, add the nitric acid of 2 grams, 65 weight % and the hydrochloric acid of 2 grams, 36 weight % again, make H in the system
+Proton concentration is about 4.4mol/L; It is complete to leave standstill the 12h postprecipitation under 20 ℃, and precipitation is used the Buchner funnel suction filtration, and drying obtains the white phosphotungstic acid of 0.29 gram, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, yield 58.0%.
Embodiment 4
Condition according to embodiment 1 reclaims heteropoly acid, and difference is that the catalyst that recycles is the support type phosphomolybdic acid catalyst of inactivation in iso-butane and the butene alkylation, and this activity of such catalysts constituent element is H
3PMo
12O
40, carrier is an active carbon, contains phosphomolybdic acid 35 weight %; Organic solvent is an acetone; Add salpeter solution and under 75 ℃, leave standstill 0.5h; Obtain the yellow phosphomolybdic acid of 1.90 grams at last, yield 54.3%.Its
31The P-NMR nuclear magnetic resoance spectrum is seen Fig. 3.Have only the peak of a chemical shift at-4.01ppm place among Fig. 3, it is the phosphomolybdic acid H with single structure
3PMo
12O
40Middle phosphorus atoms
31The P-NMR nuclear magnetic resonance peak; As can be seen from Figure 3, the phosphide that does not have other structure in the sample.
Condition according to embodiment 1 reclaims heteropoly acid, and difference is that the catalyst that recycles is the load type silicotungstic acid catalyst of inactivation in iso-butane and the butene alkylation, and this activity of such catalysts constituent element is silico-tungstic acid H
4SiW
12O
40, carrier is an aluminium oxide, contains silico-tungstic acid weight 30%; Organic solvent is an acetate, and it is 140 ℃ that the temperature of removing acetate is steamed in oil bath, and adding concentration in this filtrate is nitric acid 5.9 grams of 65 weight %, and the concentration that makes nitric acid in the system is with H
+Count about 2.5mol/L.Obtain the highly purified silico-tungstic acid of 1.49 grams at last, yield 49.7%.Its
29The Si-NMR nuclear magnetic resoance spectrum is seen Fig. 4.Have only the peak of a chemical shift at-84.912ppm place among Fig. 4, it is the silico-tungstic acid H with single structure
4SiW
12O
40Middle silicon atom
29The Si-NMR nuclear magnetic resonance peak; As can be seen from Figure 4, the silicide that does not have other structure in the sample.
Embodiment 6
Condition according to embodiment 1 reclaims heteropoly acid, and difference is: the filtrate after the heteropoly acid precipitation is used as the sour scarvenger that reclaims heteropoly acid next time.Condition according to embodiment 1 reclaims heteropoly acid for the second time, and the filtrate after precipitating with heteropoly acid is as sour scarvenger.Filtrate cycle is used three times, and the average yield of heteropoly acid reaches 60.8%.The results are shown in Table 1, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar.
Table 1
Embodiment 7
Take by weighing the carried phospho-tungstic acid catalyst of 1O gram inactivation in the benzene alkylation with ethylene reaction, this activity of such catalysts constituent element is a phosphotungstic acid, and carrier is a silicon oxide sio
2, containing phosphotungstic acid 20 weight %, step and condition recovery phosphotungstic acid according to embodiment 1 obtain the white phosphotungstic acid of 1.16 grams, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 58%.
Embodiment 8
Take by weighing the load type silicotungstic acid catalyst of 20 grams inactivation in the benzene alkylation with ethylene reaction, this activity of such catalysts constituent element is a silico-tungstic acid, and carrier is a silicon oxide sio
2, contain silico-tungstic acid 25 weight %.Condition according to embodiment 1 reclaims silico-tungstic acid, and difference is to add nitric acid 30 grams that concentration is 65 weight % in this filtrate, and the concentration that makes nitric acid in the system is with H
+Count about 7.4mol/L; Obtain the white silico-tungstic acid of 2.71 grams, yield is 54.2%, its
29Si-NMR nuclear magnetic resoance spectrum and Fig. 4 are similar.
Embodiment 9
Take by weighing the carried phospho-tungstic acid catalyst of 20 grams inactivation in benzene and the reaction of 12-allylic alkylation, this activity of such catalysts constituent element is a phosphotungstic acid, and carrier is a silicon oxide sio
2, containing phosphotungstic acid 25 weight %, step and condition recovery phosphotungstic acid according to embodiment 1 obtain the white phosphotungstic acid of 2.81 grams, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 56.2%.
Take by weighing the support type phosphomolybdic acid catalyst of 20 grams inactivation in benzene and the reaction of 12-allylic alkylation, this activity of such catalysts constituent element is a phosphomolybdic acid, carrier is an active carbon, contain phosphomolybdic acid 35 weight %, step and condition according to embodiment 1 reclaim phosphomolybdic acid, obtain the yellow phosphomolybdic acid of 3.43 grams, yield is 49.0%, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 3 are similar.
Embodiment 11
Take by weighing 20 grams and carry out the carried phospho-tungstic acid catalyst of inactivation in the reaction of etherification reaction generation MTBE at methyl alcohol and isobutene, this activity of such catalysts constituent element is a phosphotungstic acid, and carrier is a silicon oxide sio
2, containing phosphotungstic acid 20 weight %, step and condition recovery phosphotungstic acid according to embodiment 1 obtain the white phosphotungstic acid of 2.42 grams, its
31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 60.5%.
Claims (11)
1. method that reclaims the active component heteropoly acid from the carried heteropoly acid catalyst of inactivation, contain following steps:
(1), the carried heteropoly acid catalyst of inactivation is contacted with organic solvent, heteropoly acid is dissolved in the organic solvent, isolates carrier, obtain heteropoly acid organic solution A;
(2), the organic solvent among the separation solution A, residue is dissolved in the water, obtain heteropoly acid aqueous solution B;
(3), aqueous solution B is mixed with sour scarvenger, make heteropoly acid purifying precipitation, filter, drying, obtain the heteropoly acid crystal, described sour scarvenger is an inorganic acid.
2. in accordance with the method for claim 1, it is characterized in that the active component heteropoly acid in the described carried heteropoly acid catalyst is phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or silicomolybdic acid.
3. in accordance with the method for claim 1, it is characterized in that the carrier in the described carried heteropoly acid catalyst is the mixture or the active carbon of silica, aluminium oxide, silica-alumina.
4. in accordance with the method for claim 1, it is characterized in that the described organic solvent of step (1) is the organic polar solvent that can dissolve each other with water.
5. in accordance with the method for claim 4, it is characterized in that the described organic solvent of step (1) is selected from one or more the mixture in methyl alcohol, ethanol, acetone and the acetate.
6. in accordance with the method for claim 1, it is characterized in that the consumption of the described water of step (2) is 0.4-10 a times of heteropoly acid weight.
7. in accordance with the method for claim 1, it is characterized in that the described sour scarvenger of step (3) is hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary proportion of hydrochloric acid, sulfuric acid and nitric acid.
8. in accordance with the method for claim 1, it is characterized in that the concentration of sour scarvenger in the mixed solution of aqueous solution B and sour scarvenger is with H
+Count 0.1～8.0mol/L.
9. in accordance with the method for claim 1, it is characterized in that the concentration of described sour scarvenger in the mixed solution of aqueous solution B and sour scarvenger is with H
+Count 0.5～6.0mol/L.
10. in accordance with the method for claim 1, it is characterized in that the described purifying of step (3) is deposited in 0～80 ℃ to carry out.
11. in accordance with the method for claim 1, it is characterized in that the described purifying of step (3) is deposited in 5～50 ℃ to carry out.
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