CN101209427B - 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 PDF

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CN101209427B
CN101209427B CN 200610169668 CN200610169668A CN101209427B CN 101209427 B CN101209427 B CN 101209427B CN 200610169668 CN200610169668 CN 200610169668 CN 200610169668 A CN200610169668 A CN 200610169668A CN 101209427 B CN101209427 B CN 101209427B
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acid
heteropoly acid
catalyst
heteropoly
accordance
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CN 200610169668
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CN101209427A (en
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杜勇
何奕工
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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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 water to cause the heteropoly acid to dissolve into the organic solvent so as to get a carrier through separation, thus obtaining heteropoly acid water solution;(2) the heteropoly acid water solution contacts 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 organic solvent, gases containing oxygen, oxyful as well as an ion exchange method, and the yield can reach 70 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

A kind of method that from the carried heteropoly acid catalyst of inactivation, reclaims heteropoly acid

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.(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.Covered byproduct of reaction on the catalyst surface,, reactive activity has been reduced significantly as macromolecular organic matter, coke precursor thing.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 carried heteropoly acid catalyst active component heteropoly acid 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 separates some structure of back from catalyst carrier and changes, 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 as the preparation 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 not with an organic solvent, 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 water effect of described inactivation, and the heteropoly acid in the catalyst pores is dissolved in the water, isolate carrier, obtain the heteropoly acid aqueous solution; Add inorganic acid 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 water, heteropoly acid is dissolved in the water, isolate carrier, obtain the heteropoly acid aqueous solution;

(2), the heteropoly acid aqueous solution contacts with inorganic acid, makes heteropoly acid purifying precipitation, filters, drying, obtains the heteropoly acid crystal.

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 water is the water that does not contain other ion substantially, includes but not limited to deionized water, distilled water or electrodialytic water; The consumption of water 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 water, general consumption be catalyst weight 1-10 doubly, preferred 2-5 is doubly; The temperature that catalyst contacts with water can be more than the freezing point of water to 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, heteropoly acid is dissolved in the water.

In step (1), can be by the method carrier of separating such as filtering, centrifugal.

In step (2), the preferred hydrochloric acid of described inorganic acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio.Described inorganic acid can be the aqueous solution.The consumption of inorganic acid is wanted can make the heteropoly acid precipitation fully at least, and the concentration of inorganic acid in the mixed solution of the heteropoly acid aqueous solution and inorganic acid is with H generally speaking +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 concentration of aqueous solution, inorganic acid concentration and the temperature correlation of purifying precipitation were generally finished in 10 minutes~120 hours, and the time is long again, and is unfavorable in suitability for industrialized production; The preferred sedimentation time is 1-48 hour.With sedimentation and filtration, drying, just obtain highly purified heteropoly acid crystal.

Inorganic acid can recycle, and can further improve the yield of heteropoly acid.

In step (2) before, in order to reduce the inorganic acid consumption, the heteropoly acid aqueous solution can also be concentrated.The mode that concentrates can be any known or unknown method that can realize this purpose, and usual way is distillation, can be air-distillation, decompression distillation etc.The degree that concentrates can both can distill small part water in very wide scope adjustment, also can distill most of water; In order to reduce the inorganic acid consumption, preferred operation is to make the heteropoly acid aqueous solution water content after concentrating be the initial 2%-20% that adds the water yield.

Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:

(1) removal process not with an organic solvent, oxygen-containing gas, hydrogen peroxide, do not use ion-exchange process yet, flow process is simple, the yield height, 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 patent of 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; Yagasaki A, Ichida H.Polyhed.1988,7:1131.Patent of 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 5 phosphomolybdic acid samples 31The P-NMR nuclear magnetic resoance spectrum.

Fig. 4 is embodiment 6 silico-tungstic acid samples 29The Si-NMR nuclear magnetic resoance spectrum.

The specific embodiment

By direct elaboration in this 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 are analysis, and Beijing chemical reagents corporation produces.

Embodiment 1

Take by weighing the carried phospho-tungstic acid catalyst of 20 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is H 3PW 12O 40, carrier is a silicon oxide sio 2, contain phosphotungstic acid 25 weight %, this catalyst is put into conical flask, add 40g water, on magnetic stirring apparatus, fully stir, the temperature of the hierarchy of control is 25 ℃, handles 1 hour.Suction filtration is removed carrier; At 55 ℃, 15.75 * 10 3Under the condition of Pa with solution concentration to 20ml; Add concentration then and be nitric acid 18.8 grams of 65 weight %, make in the system concentration of nitric acid with H +Count 5.8mol/L; It is complete to leave standstill the 48h postprecipitation under 30 ℃, and after precipitation was used the Buchner funnel suction filtration, drying obtained the white phosphotungstic acid of 3.46 grams, with H 3PW 12O 40Meter, yield is 69.2%.

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 phospho-tungstic acid catalyst of 20 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is H 3PW 12O 40, carrier is a silicon oxide sio 2, contain phosphotungstic acid 25 weight %, this catalyst is put into conical flask, add 40g water, on magnetic stirring apparatus, fully stir, the temperature of the hierarchy of control is 25 ℃, handles 1 hour.Suction filtration is removed carrier; At 55 ℃, 15.75 * 10 3Under the condition of Pa with solution concentration to 20ml; 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 phospho-tungstic acid catalyst of 20 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is a phosphotungstic acid, content 25 weight %, and carrier is a silicon oxide sio 2This catalyst is put into conical flask, add 20g water, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 25 ℃, handles 5 hours.Suction filtration is removed carrier; Add concentration then and be nitric acid 18.8 grams of 65 weight %, make in the system concentration of nitric acid with H +Count 5.8mol/L; It is complete to leave standstill the 48h postprecipitation under 30 ℃, and after precipitation was used the Buchner funnel suction filtration, drying obtained the white phosphotungstic acid of 2.35 grams, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 47.0%.

Embodiment 3

Take by weighing the carried phospho-tungstic acid catalyst of 50 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is a phosphotungstic acid, and carrier is a silicon oxide sio 2, contain phosphotungstic acid 25 weight %.This catalyst is put into conical flask, add 80g water, fully stir on magnetic stirring apparatus, hierarchy of control temperature is 80 ℃, reflow treatment 110 hours.Suction filtration is removed carrier; At 55 ℃, 15.75 * 10 3Under the condition of Pa with solution concentration to 20ml.Adding concentration in concentrating good solution is sulfuric acid 0.5 gram of 96 weight %, makes in the system sulfuric acid concentration with H +Count 0.5mol/L; Leave standstill the 110h precipitation fully under 5 ℃, after precipitation was used the Buchner funnel suction filtration, drying obtained the white phosphotungstic acid of 7.6 grams, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 60.8%.

Embodiment 4

Take by weighing the carried phospho-tungstic acid catalyst of 20 grams inactivation in iso-butane and butene alkylation, this activity of such catalysts constituent element is a phosphotungstic acid 0, carrier is a silicon oxide sio 2, contain phosphotungstic acid 25 weight %.This catalyst is put into conical flask, add 200g water, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 10 ℃, handles 24 hours.Suction filtration is removed carrier; At 70 ℃, 31.25 * 10 3Under the condition of Pa with solution concentration to 20ml.In concentrating good solution, add 10 gram nitration mixture (nitric acid of 5 grams, 65 weight %, the hydrochloric acid of 5 grams, 36 weight %), make in the system nitration mixture concentration with H +Count 3.6mol/L; It is complete to leave standstill the 12h postprecipitation under 20 ℃; Suction filtration, drying obtains the white phosphotungstic acid of 3.4 grams, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, yield 68.0%.

Embodiment 5

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, content 35 weight %, carrier is an active carbon; Add salpeter solution and under 75 ℃, leave standstill 0.5h; Obtain 4.34 gram phosphomolybdic acids at last, yield 62.0%.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 to have phosphorus atoms in the phosphomolybdic acid of single structure 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.

Embodiment 6

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 H 4SiW 12O 40, content 30 weight %, carrier is an aluminium oxide; The water yield that adds during processing is 30g; The inorganic acid that adds is that concentration is nitric acid 5.9 grams of 65 weight %, and concentration of nitric acid is with H in the system +Count 2.5mol/L; Obtain 3.5 gram silico-tungstic acids at last, yield 58.3%.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 7

Condition according to embodiment 1 reclaims heteropoly acid, and difference is: the filtrate after the heteropoly acid precipitation is used as the inorganic acid 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 inorganic acid.Filtrate cycle is used three times, and the average yield of heteropoly acid reaches 72.9%.The results are shown in Table 1, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar.

Table 1

Embodiment 8

Take by weighing the carried phospho-tungstic acid catalyst of 20 grams inactivation in the benzene alkylation with ethylene reaction, this activity of such catalysts constituent element is a phosphotungstic acid, content 20 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phosphotungstic acid, obtain the white phosphotungstic acid of 2.68 grams, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 67%.

Embodiment 9

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, content 25 weight %, and carrier is a silicon oxide sio 2Condition according to embodiment 1 reclaims silico-tungstic acid, and difference is that the inorganic acid that adds is that concentration is nitric acid 30 grams of 65 weight %, and the concentration of nitric acid is with H in the system +Count 7.4mol/L; Obtain the white silico-tungstic acid of 3.24 grams, yield is 64.8%, its 29Si-NMR nuclear magnetic resoance spectrum and Fig. 4 are similar.

Embodiment 10

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, content 25 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phosphotungstic acid, obtain the white phosphotungstic acid of 3.27 grams, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 65.4%.

Embodiment 11

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, and content is 35 weight %, and carrier is an active carbon.Step and condition according to embodiment 1 reclaim phosphomolybdic acid, obtain the yellow phosphomolybdic acid of 4.21 grams, and yield is 60.1%, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 3 are similar.

Embodiment 12

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 content is 20 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phosphotungstic acid, obtain the white phosphotungstic acid of 2.78 grams, its 31P-NMR nuclear magnetic resoance spectrum and Fig. 1 are similar, and yield is 69.5%.

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 water, heteropoly acid is dissolved in the water, isolate carrier, obtain the heteropoly acid aqueous solution;
(2), the heteropoly acid aqueous solution contacts with inorganic acid, makes heteropoly acid purifying precipitation, filters, drying, obtains the heteropoly acid crystal.
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 consumption of the middle water of step (1) is 1-10 a times of catalyst weight.
5. in accordance with the method for claim 4, it is characterized in that the consumption of the middle water of step (1) is 2-5 a times of catalyst weight.
6. in accordance with the method for claim 1, it is characterized in that the described inorganic acid of step (2) is hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio.
7. in accordance with the method for claim 1, it is characterized in that the concentration of the described inorganic acid of step (2) in the mixed solution of the heteropoly acid aqueous solution and inorganic acid is counted 0.1~8.0mol/L with H+.
8. in accordance with the method for claim 7, it is characterized in that the concentration of the described inorganic acid of step (2) in the mixed solution of the heteropoly acid aqueous solution and inorganic acid is counted 0.5~6.0mol/L with H+.
9. in accordance with the method for claim 1, it is characterized in that the described purifying of step (2) is deposited in 0~80 ℃ to carry out.
10. in accordance with the method for claim 9, it is characterized in that the described purifying of step (2) is deposited in 5~50 ℃ to carry out.
11. in accordance with the method for claim 1, it is characterized in that, in step (2) before, the heteropoly acid aqueous solution is concentrated.
CN 200610169668 2006-12-27 2006-12-27 Method for recovering heteropoly acid from deactivation supported type heteropoly acid catalyst CN101209427B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1142638A1 (en) * 2000-04-06 2001-10-10 Nippon Shokubai Kagaku Kogyo Kabushiki Kaisha Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid
CN1354044A (en) * 2001-12-15 2002-06-19 大连理工大学 Method for recovering heteropolyacid catalyst
JP2002302468A (en) * 2001-04-04 2002-10-18 Teijin Ltd Method for collecting catalyst from diarylcarbonate- containing reaction mixture solution
CN1526707A (en) * 2003-03-03 2004-09-08 中国科学院大连化学物理研究所 Homogeneous catalyst recovering process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1142638A1 (en) * 2000-04-06 2001-10-10 Nippon Shokubai Kagaku Kogyo Kabushiki Kaisha Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid
JP2002302468A (en) * 2001-04-04 2002-10-18 Teijin Ltd Method for collecting catalyst from diarylcarbonate- containing reaction mixture solution
CN1354044A (en) * 2001-12-15 2002-06-19 大连理工大学 Method for recovering heteropolyacid catalyst
CN1526707A (en) * 2003-03-03 2004-09-08 中国科学院大连化学物理研究所 Homogeneous catalyst recovering process

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