CN101376526B - Method for recovering heteropoly acid from deactivated supported type heteropoly acid catalyst - Google Patents

Method for recovering heteropoly acid from deactivated supported type heteropoly acid catalyst Download PDF

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CN101376526B
CN101376526B CN2007101211902A CN200710121190A CN101376526B CN 101376526 B CN101376526 B CN 101376526B CN 2007101211902 A CN2007101211902 A CN 2007101211902A CN 200710121190 A CN200710121190 A CN 200710121190A CN 101376526 B CN101376526 B CN 101376526B
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acid
heteropolyacid
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heteropoly acid
catalyst
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CN101376526A (en
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杜勇
何奕工
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention provides a method for recovering an active component heteropoly acid from an inactive supported heteropoly acid catalyst, which comprises the steps as follows: (1) a catalyst to be processed contacts with an oxidizer-containing water solution; (2) the above-mentioned system is processed in an oxygen-containing atmosphere; (3) the processed heteropoly acid catalyst is dissolved in water or an organic polar solvent, and a heteropoly acid solution A and a heteropoly acid solution B are obtained respectilvey after a carrier is separated out; (4) the organic polar solvent is separated from the heteropoly acid solution B; remainders are dissolved in water to obtain a heteropoly acid solution C; and (5) the heteropoly acid solution A or the heteropoly acid solution C contacts with an inorganic acid to lead the heteropoly acid to be purified and precipitated, and a heteropoly acid crystal is obtained through filtration and drying. Compared with the prior art, the method has simple flow and is suitable for the application in a large-scale industry, and the coefficient of recovery can reach about 95 percent; the recovered heteropoly acid has high purity quotient, and can satisfy the requirement for preparing a novel supported catalyst.

Description

A kind of method that from the carried heteropoly acid catalyst of inactivation, reclaims heteropolyacid
Technical field
The present invention relates to a kind of method that reclaims heteropolyacid, more particularly, the present invention relates to a kind of method that from the carried heteropoly acid catalyst of inactivation, reclaims heteropolyacid.
Background technology
Heteropolyacid is the class acid that, condensation acidified by two or more inorganic oxygen-containing acid ion, dehydration obtain having cagelike structure and duct, the heteropolyacid of this class formation had both had strongly-acid, has oxidation-reduction quality again, therefore acid catalyst can be used as, also redox catalyst can be used as.Heteropolyacid is loaded on the carrier equably, on silicon oxide, aluminum oxide, silica-alumina mixture or gac, 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).Heteropolyacid has multiple structure, but in order effectively to control the activity and the selectivity of heteropolyacid catalyst, what generally use all is the heteropolyacid of single structure.Phospho-wolframic acid is most widely used in heteropolyacid catalyst, and is also the most representative.In addition, also have phospho-molybdic acid, silicotungstic acid, silicomolybdic acid and molybdovanaphosphoric acid Mo 10V 0-3P 0.8-5X 0-3Y 0-3O e(X is that basic 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 is used this class carried heteropoly acid catalyst, unavoidably has the problem of catalyst deactivation.The reason of inactivation has catalyzer to be heated to cause that catalyst backbone is destroyed, catalyst surface is sticked by reaction product or by product; Basic metal on the support of the catalyst also can influence the activity of heteropolyacid.Sticked byproduct of reaction on the catalyst surface,, reactive activity has been reduced significantly as macromolecular organism, coke precursor thing.Carried heteropoly acid catalyst behind the inactivation can't continue to use.
Various heteropolyacids all are expensive chemical productss, if can reclaim the active component heteropolyacid in the carried heteropoly acid catalyst of inactivation, utilize its preparation catalyzer again, just can reduce the Preparation of catalysts cost greatly.In addition, the carried heteropoly acid catalyst of inactivation still has strongly-acid, if random landfill and abandoning, the heteropolyacid on the catalyzer can the severe contamination underground water source.Therefore, no matter the active component heteropolyacid in the carried heteropoly acid catalyst of recovery inactivation is from reducing the Preparation of catalysts cost, still saying from point of view of environment protection, all significant.
The inventor finds, the heteropolyacid that loads on the single structure on the support of the catalyst separates some structure of back from support of the catalyst and changes, promptly generate the heteropolyacid of multiple structure, the heteropolyacid of this multiple structure can not satisfy the requirement of preparation carried heteropoly acid catalyst.
Heteropolyacid on the carried heteropoly acid catalyst of recovery inactivation, heteropolyacid is more dissolved from support of the catalyst, its less important heteropolyacid that makes separates with carrier and solvent phase, at last, take measures to obtain the heteropolyacid of highly purified single structure, just can be used to prepare carried heteropoly acid catalyst once more.
How to reclaim heteropolyacid more, improving the rate of recovery and obtaining highly purified heteropolyacid with single structure becomes a main difficult problem that reclaims heteropolyacid.
CN1102438C discloses a kind of low-temp recovery method of solid acid alkylation catalysts, this method is to treat that the said catalyzer of regenerated contacts more than 10 minutes with the aqueous solution that contains at least a oxygenant, handled 0.5-10 hour under 100-250 ℃ temperature in the atmosphere of air, oxygen or their gas mixture then, wherein said oxygenant comprises HClO for being selected from 4, KClO 4, NH 4ClO 4, and NaClO 4At interior perchloric acid and water-soluble salt thereof, comprise HClO, KClO, NH 4ClO and NaClO are at interior hypochlorous acid and water-soluble salt and H 2O 2And/or HNO 3Can under lower temperature, effectively remove the macromole coke precursor of catalyst surface and not destroy catalyst structure according to the method that this invention provides, make activity and selectivity level before catalyzer returns to regeneration.
JP56163755 discloses a kind of containing at least of catalyzed alkene hydration and aldehyde gas phase oxidation a kind of load phospho-molybdic acid or the heteropolyacid catalyst renovation process of molybdovanaphosphoric acid or their salt that is applied to.Support of the catalyst is silicon oxide, aluminum oxide, diatomite or activated carbon.This method water or water and methanol mixed act on the carried heteropoly acid catalyst of this inactivation, and the heteropolyacid that loads on the catalyzer is dissolved in the solvent, after the filtration, feed the gas of molecule-containing keto in filtrate, and the catalytic activity of heteropolyacid is recovered substantially; The heteropolyacid solution that this catalytic activity is recovered substantially is adjusted to finite concentration and loads on the carrier, can make catalyzer once more.This patent does not disclose the rate of recovery of heteropolyacid 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 phospho-molybdic acid or the heteropolyacid catalyst renovation process of molybdovanaphosphoric acid and salt thereof that is applied to.Support of the catalyst is diatomite, ceramic fiber or carbon fiber.This method water or water and water-miscible organic solvent mixing effect are in the carried heteropoly acid catalyst of this inactivation, and the heteropolyacid that loads on the catalyzer is dissolved in water or the solvent; Remove by filter insoluble carrier then, in solution, add hydrogen peroxide to solution again and become orange, in filtrate, add the crystalline metaantimmonic acid then and carry 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 heteropolyacid the complete evaporation drying of filtrate.This patent does not also disclose the rate of recovery of heteropolyacid and the data of purity.
Summary of the invention
The invention provides a kind of method that reclaims the active component heteropolyacid from the carried heteropoly acid catalyst of inactivation, the heteropolyacid crystalline structure that this method adopts simple recycling step to obtain is single, rate of recovery height.
Characteristics of the present invention are at first the carried heteropoly acid catalyst of described inactivation is contacted with the aqueous solution that contains oxygenant; Above-mentioned system is handled certain hour under certain temperature in oxygen-containing atmosphere; Make carried heteropoly acid catalyst and the water or the organic polar solvent effect of the inactivation of above-mentioned processing, the heteropolyacid in the catalyst pores is dissolved in water or the organic polar solvent, isolate carrier, obtain heteropolyacid water solution A or polar organic solution B; Separate the organic polar solvent in the polar organic solution B, residuum is dissolved in the water, obtain heteropolyacid aqueous solution C; Add mineral acid in heteropolyacid solution A or C, make heteropolyacid purifying precipitation, filtration, drying obtain the single heteropolyacid crystal of structure then.
This method that reclaims the active component heteropolyacid from the carried heteropoly acid catalyst of inactivation contains following steps:
(1), pending catalyzer is contacted with the aqueous solution that contains oxygenant;
(2), this system is handled in oxygen-containing atmosphere;
(3), the heteropolyacid catalyst of above-mentioned processing is contacted with water or organic polar solvent, make heteropolyacid dissolving, isolate carrier, obtain heteropolyacid water solution A or polar organic solution B;
(4), the organic polar solvent among the separation solution B, residuum is dissolved in the water, obtain the heteropolyacid solution C;
(5), heteropolyacid solution A or C are contacted with mineral acid, make heteropolyacid purifying precipitation, filter, drying, obtain the heteropolyacid 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 heteropolyacid obtain on the mixture of silicon oxide, aluminum oxide, silica-alumina or gac through uniform loading described carried heteropoly acid catalyst, heteropolyacid wherein is the acid that a class that, condensation acidified by two or more inorganic oxygen-containing acid ion, dehydration obtain having cagelike structure and duct has single structure, includes but not limited to phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid of various single structures etc.
In step (1), described oxygenant comprises HClO for being selected from 4, KClO 4, NH 4ClO 4, and NaClO 4At interior perchloric acid and water-soluble salt thereof, comprise HClO, KClO, NH 4ClO and NaClO are at interior hypochlorous acid and water-soluble salt and H 2O 2And/or HNO 3Total consumption of oxygenant is 10～160 weight % of said catalyst weight, preferred 20～150 weight %.The concentration of described aqueous oxidizing agent solution is 10～80 weight %.Oxygenant contacts at normal temperatures with catalyzer, and duration of contact is preferably more than 10 minutes, general 0.5-2 hour.
In step (2), described oxygen-containing atmosphere is air, oxygen or their mixed atmosphere.Under this atmosphere, treatment temp is at 100-250 ℃, and preferred 120-230 ℃, the treatment time is more than 0.5 hour, preferred 1-5 hour.
The oxygenant that the described total consumption of step (1) is 10～160 weight % of said catalyst weight can once add, and also can add several times.Each oxygenant add-on can be identical or different, all contacts more than 10 minutes after adding oxygenant at every turn, carries out step (2) again, handles more than 0.5 hour in oxygen-containing atmosphere.
In step (3), described water is not contain or do not contain other ionic water substantially, can be tap water, is preferably pure water, includes but not limited to deionized water, distilled water or electrodialytic water; Described organic polar solvent is the organic polar solvent that can dissolve each other with water, includes but not limited to one or more the mixture in methyl alcohol, ethanol, acetone and the acetate.
In step (3), the consumption of described water or organic polar solvent is greater than the heteropolyacid that is contained in the carried heteropoly acid catalyst of inactivation and forms the required consumption of saturated solution in solvent, general consumption be catalyst weight 1-10 doubly, preferred 2-5 is doubly; The temperature that catalyzer contacts with water or organic polar solvent can be more than the zero pour of water or organic polar solvent 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.Duration of contact can according to the way of contact with contact temperature decision, to guarantee that finally heteropolyacid is dissolved in water or the organic polar solvent fully.
In step (3), can be by the method carrier of separating such as filtering, centrifugal.
In step (4), the method of separating organic solvent can be any known or unknown method that can realize this purpose, and usual method 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 (5), described mineral acid is selected from hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio.Described mineral acid generally is mixed with the aqueous solution.The consumption of mineral acid is wanted can make the heteropolyacid precipitation fully at least, and the concentration of mineral acid in the mixing solutions of the heteropolyacid aqueous solution and mineral 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 ℃; The sedimentary speed of purifying and heteropolyacid concentration of aqueous solution, inorganic acid concentration and temperature correlation were generally finished in 10 minutes～120 hours, and the time is long again, and is unfavorable in suitability for industrialized production; Preferred sedimentation time is 1-48 hour.With sedimentation and filtration, drying, just obtain highly purified heteropolyacid crystal.
Mineral acid can recycle, and can further improve the yield of heteropolyacid.
In step (5) before, in order to reduce the mineral acid consumption, the heteropolyacid aqueous solution can also be concentrated.Spissated mode can be any known or unknown method that can realize this purpose, and usual method is distillation, can be air distillation, underpressure distillation etc., and the heteropolyacid solution water content after concentrating is generally the 2%-50% of the initial water yield.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
(1) recovery process is simple, and yield is very high, and suitability for mass industrialized is used;
(2) the heteropolyacid 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 phospho-wolframic acid, phospho-molybdic acid compound purity, referring to document: J.Inorg.Chem., and 1977,16 (11): 2916; The nuclear magnetic resonance spectrum of the phosphorus atom of different chemical environment has the characteristic peak of different chemical displacement, and patent of the present invention adopts 31P-NMR nucleus magnetic resonance spectral method is identified the phospho-wolframic acid that reclaims, the purity of phospho-molybdic acid.
Similarly, 29Si-NMR, 95The Mo-NMR nmr analysis also is a kind of classical way of identifying silicotungstic acid, silicomolybdic acid compound purity, referring to document: J.Phys.Chem.1989,95:904; YagasakiA, Ichida H.Polyhed.1988,7:1131.Patent of the present invention adopts this method to identify the silicotungstic acid that reclaims, the purity of silicomolybdic acid.
Fig. 1 is embodiment 1 a phospho-wolframic acid sample 31The P-NMR nuclear magnetic resonance spectrum.
Fig. 2 is Comparative Examples 2 phospho-wolframic acid samples 31The P-NMR nuclear magnetic resonance spectrum.
Fig. 3 is embodiment 5 phospho-molybdic acid samples 31The P-NMR nuclear magnetic resonance spectrum.
Fig. 4 is embodiment 6 silicotungstic acid samples 29The Si-NMR nuclear magnetic resonance spectrum.
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%, analytical pure, and the Beijing Chemical Plant produces; HClO 4, NH 4ClO 4, NaClO, H 2O 2The aqueous solution, sulfuric acid, nitric acid, methyl alcohol, ethanol, acetone, acetate are analytical pure, and Beijing chemical reagents corporation produces.
Embodiment 1
Take by weighing the carried phospho-tungstic acid catalyzer of 20 grams inactivation in Trimethylmethane and butene alkylation, this activity of such catalysts constituent element is H 3PW 12O 40, carrier is a silicon oxide sio 2, containing phospho-wolframic acid 25 weight %, this catalyzer of adding and isopyknic concentration are the HClO of 35 weight % in crucible 4The aqueous solution 25.1 grams make the lucky complete wetting of catalyzer, make HClO 4Consumption be 44% of catalyzer dry basis, after placing 0.5h, above-mentioned system is put into retort furnace at 230 ℃ of calcination 1h (air atmosphere), catalyzer after will so handling after the cooling is put into Erlenmeyer flask, add 40g water, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 25 ℃, handles 1 hour.Suction filtration is removed carrier; 55 ℃, reduce pressure 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 B suction filtration, drying obtained the white phospho-wolframic acid of 4.75 grams, with H 3PW 12O 40Meter, yield is 95.0%.
The sample phospho-wolframic acid 31The P-NMR nuclear magnetic resonance spectrum is seen Fig. 1.Have only the peak of a chemical shift at-14.860ppm place among Fig. 1, it is the phospho-wolframic acid H with single structure 3PW 12O 40Middle phosphorus atom 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
The loaded catalyst kind of inactivation is identical with embodiment 1 with consumption.Catalyzer is put into Erlenmeyer flask, add 40g water, fully stir on magnetic stirring apparatus, the temperature of the hierarchy of control is 25 ℃, handles 1 hour.Suction filtration is removed carrier; 55 ℃, reduce pressure 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 B suction filtration, drying obtained the white phospho-wolframic acid of 3.47 grams, with H 3PW 12O 40Meter, yield is 69.4%.
The explanation of this Comparative Examples has lacked step (1) and (2), and the rate of recovery of heteropolyacid obviously descends.
Comparative Examples 2
The loaded catalyst kind of inactivation is identical with embodiment 1 with consumption.This catalyzer of adding and isopyknic concentration are the HClO of 35 weight % in crucible 4The aqueous solution makes the lucky complete wetting of catalyzer, makes HClO 4Consumption be respectively 44% of catalyzer dry basis, after placing 0.5h, above-mentioned system is put into retort furnace at 230 ℃ of calcination 1h, catalyzer after will so handling after the cooling is put into Erlenmeyer flask, add 40g water, fully stir on magnetic stirring apparatus, 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 nucleus magnetic resonance.
Fig. 2 is Comparative Examples 2 phospho-wolframic acid samples 31The P-NMR nuclear magnetic resonance spectrum.Be the phospho-wolframic acid H of single structure at the peak at chemical shift-14.791ppm place among Fig. 2 3PW 12O 40Middle phosphorus atom 31The P-NMR nuclear magnetic resonance peak; At the peak at chemical shift 0.361ppm place is phosphorus atom in the phosphate radical 31The P-NMR nuclear magnetic resonance peak; Chemical shift-10.656ppm to several small peaks that-13.405ppm (account for phosphorus atom sum 33.05%) locates to occur are heteropolyacid phosphorus atom of other structure 31The P-NMR nuclear magnetic resonance peak.
The explanation of this Comparative Examples lacks step (5), and the purity of the heteropolyacid of recovery obviously descends.
Embodiment 2
The carried phospho-tungstic acid catalyzer of inactivation is with embodiment 1, and consumption 50 restrains.Adding this catalyzer and 16.3g concentration in crucible respectively is the HClO of 15 weight % 4Solution, and 15.0g concentration is the HNO of 15 weight % 3Solution stirs behind the placement 0.5h, and above-mentioned system is put into retort furnace at 120 ℃ of calcination 3h (oxygen atmosphere), and adding 16.3g concentration again in this catalyzer after the taking-up cooling is the HClO of 15 weight % 4Solution and 15.0g concentration are the HNO of 15 weight % 3Solution is placed and is put into retort furnace after 30 minutes again at 120 ℃ of calcination 3h (oxygen atmosphere), and the catalyzer after so handling is put into Erlenmeyer flask, adds 50g methyl alcohol, fully stirs, and 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 heteropolyacid; Add this steaming excess of 5g water dissolution,, 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 vitriolic H in the system +Proton concentration is about 0.6mol/L; Leave standstill 110h under 5 ℃, after precipitation was used the B suction filtration, drying obtained the white phospho-wolframic acid of 12.1 grams, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar, with H 3PW 12O 40Meter, yield is 96.8%.
Embodiment 3
Take by weighing the carried heteropoly acid catalyst of 2 grams inactivation in Trimethylmethane and butene alkylation, this activity of such catalysts constituent element is phospho-wolframic acid H 3PW 12O 40, content is 25 weight %, carrier is silica-alumina mixture, i.e. SiO 2-Al 2O 3This catalyzer of adding and 2g concentration are the HNO of 40 weight % in crucible 3The aqueous solution stirs behind the placement 0.5h, and above-mentioned system is put into retort furnace at 175 ℃ of calcination 2.5h (oxygen atmosphere), repeats 3 times again.After taking out cooling this catalyzer is put into Erlenmeyer 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 heteropolyacid; Add 6g water dissolution heteropolyacid 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 B suction filtration, and drying obtains the white phospho-wolframic acid of 0.47 gram, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar, with H 3PW 12O 40Meter, yield 94.0%.
Embodiment 4
The carried phospho-tungstic acid catalyzer of inactivation is with embodiment 1, and consumption 20 restrains.This catalyzer of adding and isopyknic concentration are the H of 38 weight % in crucible 2O 2About 25.1 grams of the aqueous solution make the lucky complete wetting of catalyzer, place after 10 minutes, and above-mentioned system is put into retort furnace at 120 ℃ of calcination 2.0h (air atmosphere), repeat above-mentioned processing 2 times.Catalyzer after will so handling after the cooling is put into Erlenmeyer flask, adds 40g water, fully stirs on magnetic stirring apparatus, and the temperature of the hierarchy of control is 25 ℃, handles 1 hour.Suction filtration is removed carrier; 55 ℃, reduce pressure 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 B suction filtration, drying obtained the white phospho-wolframic acid of 4.75 grams, with H 3PW 12O 40Meter, yield is 95.5%.
Embodiment 5
The catalyzer of recycling is the loading type phospho-molybdic acid catalyzer of inactivation in 20g Trimethylmethane and the butene alkylation, and this activity of such catalysts constituent element is H 3PMo 12O 40, carrier is a gac, contains phospho-molybdic acid 35 weight %; This catalyzer of adding and isopyknic concentration are the NH of 65.4 weight % in crucible 4ClO 4The aqueous solution 25.1 grams make NH 4ClO 4Consumption be 150% of catalyzer dry basis, placed 60 minutes; 200 ℃ of calcination temperatures, only carry out once at the 3 hours time (mixed atmosphere).Organic solvent is an acetone; Add 20g water dissolution heteropolyacid and steam excess, add salpeter solution and under 75 ℃, leave standstill 0.5h; Obtain the yellow phospho-molybdic acid of 6.2 grams at last, yield 88.6%.Its 31The P-NMR nuclear magnetic resonance spectrum is seen Fig. 3.Have only the peak of a chemical shift at-4.000ppm place among Fig. 3, it is the phospho-molybdic acid H with single structure 3PMo 12O 40Middle phosphorus atom 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
The catalyzer of recycling is the load type silicotungstic acid catalyst of inactivation in Trimethylmethane and the butene alkylation, and this activity of such catalysts constituent element is silicotungstic acid H 4SiW 12O 40, carrier is an aluminum oxide, contains silicotungstic acid weight 30%; Adopt the incipient impregnation method, once add the NaClO that oxygenant is 52 weight %, the oxygenant add-on is 86% of a catalyzer dry basis, places 30 minutes; 200 ℃ of calcination temperatures, 3 hours time.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, it is complete to leave standstill the 48h postprecipitation under 30 ℃, obtains the highly purified silicotungstic acid of 5.42 grams at last, yield 90.3%.Its 29The Si-NMR nuclear magnetic resonance spectrum is seen Fig. 4.Have only the peak of a chemical shift at-84.910ppm place among Fig. 4, it is the silicotungstic acid H with single structure 4SiW 12O 40Middle Siliciumatom 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 heteropolyacid, and difference is: the filtrate after the heteropolyacid precipitation is used as the mineral acid that reclaims heteropolyacid next time.Condition according to embodiment 1 reclaims heteropolyacid for the second time, and the filtrate after precipitating with heteropolyacid is as mineral acid.Filtrate cycle is used three times, and the average yield of heteropolyacid reaches 96.8%.The results are shown in Table 1, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar.
Table 1
Figure G071C1190220070920D000111
Embodiment 8
Take by weighing the carried phospho-tungstic acid catalyzer of 20 grams inactivation in the benzene alkylation with ethylene reaction, this activity of such catalysts constituent element is a phospho-wolframic acid, content 20 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phospho-wolframic acid, obtain the white phospho-wolframic acid of 3.83 grams, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar, and yield is 95.8%.
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 silicotungstic acid, content 25 weight %, and carrier is a silicon oxide sio 2Condition according to embodiment 1 reclaims silicotungstic acid, and difference is that the sour purifying agent 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 silicotungstic acid of 4.82 grams, yield is 96.4%, its 29Si-NMR nuclear magnetic resonance spectrum and Fig. 4 are similar.
Embodiment 10
Take by weighing the carried phospho-tungstic acid catalyzer of 20 grams inactivation in benzene and the reaction of 12-allylic alkylation, this activity of such catalysts constituent element is a phospho-wolframic acid, content 25 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phospho-wolframic acid, obtain the white phospho-wolframic acid of 4.74 grams, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar, and yield is 94.8%.
Embodiment 11
Take by weighing the loading type phospho-molybdic acid catalyzer of 20 grams inactivation in benzene and the reaction of 12-allylic alkylation, this activity of such catalysts constituent element is a phospho-molybdic acid, and content is 35 weight %, and carrier is a gac.Step and condition according to embodiment 1 reclaim phospho-molybdic acid, obtain the yellow phospho-molybdic acid of 6.10 grams, and yield is 87.1%, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 3 are similar.
Embodiment 12
Take by weighing 20 grams and carry out the carried phospho-tungstic acid catalyzer of inactivation in the reaction of etherification reaction generation MTBE at methyl alcohol and iso-butylene, this activity of such catalysts constituent element is a phospho-wolframic acid, and content is 20 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phospho-wolframic acid, obtain the white phospho-wolframic acid of 3.87 grams, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar, and yield is 96.8%.
Embodiment 13
Take by weighing the carried phospho-tungstic acid catalyzer of 20 grams inactivation in benzene and the reaction of 12-allylic alkylation, this activity of such catalysts constituent element is a phospho-wolframic acid, content 25 weight %, and carrier is a silicon oxide sio 2Step and condition according to embodiment 1 reclaim phospho-wolframic acid, and difference is only to use the 20g water treatment, and water flushing slightly obtains about 20ml solution during suction filtration, finally obtain the white phospho-wolframic acid of 4.74 grams, its 31P-NMR nuclear magnetic resonance spectrum and Fig. 1 are similar, and yield is 94.8%.

Claims (20)

1. method that reclaims heteropolyacid from the carried heteropoly acid catalyst of inactivation, contain following steps:
(1), pending catalyzer is contacted with the aqueous solution that contains oxygenant;
(2), above-mentioned system is handled in oxygen-containing atmosphere;
(3), make the heteropolyacid catalyst of above-mentioned processing be dissolved in the water or in the organic polar solvent, isolate carrier after, obtain heteropolyacid solution A or B respectively;
(4), the organic polar solvent among the separation solution B, residuum is dissolved in the water, obtain the heteropolyacid solution C;
(5), heteropolyacid solution A or C are contacted with mineral acid, make heteropolyacid purifying precipitation, filter, drying, obtain the heteropolyacid crystal.
2. in accordance with the method for claim 1, it is characterized in that the heteropolyacid in the described carried heteropoly acid catalyst is phospho-wolframic acid, phospho-molybdic acid, silicotungstic 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 gac of silicon oxide, aluminum oxide, silica-alumina.
4. in accordance with the method for claim 1, it is characterized in that the described oxygenant of step (1) is selected from perchloric acid and water-soluble salt, hypochlorous acid and water-soluble salt thereof and H 2O 2And/or HNO 3
5. in accordance with the method for claim 1, it is characterized in that the described pending catalyzer of step (1) is more than 10 minutes with aqueous solution duration of contact of containing oxygenant.
6. in accordance with the method for claim 1, it is characterized in that total consumption of the described oxygenant of step (1) is 10～160 weight % of said catalyst weight.
7. in accordance with the method for claim 6, it is characterized in that total consumption of the described oxygenant of step (1) is 20～150 weight % of said catalyst weight.
8. in accordance with the method for claim 1, it is characterized in that the concentration of the described aqueous oxidizing agent solution of step (1) is 10～80 weight %.
9. in accordance with the method for claim 1, it is characterized in that the described oxygen-containing atmosphere of step (2) is air, oxygen or their mixed atmosphere.
10. in accordance with the method for claim 1, it is characterized in that the described treatment temp of step (2) is 100～250 ℃.
11. in accordance with the method for claim 1, it is characterized in that the described treatment time of step (2) is more than 0.5 hour, is preferably 1～5 hour.
12., it is characterized in that the described oxygenant of step (1) adds in batches according to the described method of one of claim 1 or 5-8, all contact more than 10 minutes after adding oxygenant at every turn, then carry out step (2) then.
13. in accordance with the method for claim 1, it is characterized in that described organic polar solvent is selected from one or more the mixture in methyl alcohol, ethanol, acetone and the acetate.
14., it is characterized in that the consumption of described water of step (3) or organic polar solvent is 1-10 a times of catalyst weight according to the described method in one of claim 1 or 13.
15. in accordance with the method for claim 1, it is characterized in that the described mineral acid of step (5) is hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio.
16. in accordance with the method for claim 1, it is characterized in that the concentration of the described mineral acid of step (5) in the mixing solutions of the heteropolyacid aqueous solution and mineral acid is with H +Count 0.1～8.0mol/L.
17. in accordance with the method for claim 16, it is characterized in that the concentration of the described mineral acid of step (5) in the mixing solutions of the heteropolyacid aqueous solution and mineral acid is with H +Count 0.5～6.0mol/L.
18. in accordance with the method for claim 1, it is characterized in that the described purifying of step (5) is deposited in 0～80 ℃ to carry out.
19. in accordance with the method for claim 18, it is characterized in that the described purifying of step (5) is deposited in 5～50 ℃ to carry out.
20. in accordance with the method for claim 1, it is characterized in that in step (5) before, heteropolyacid solution A or C are concentrated, the heteropolyacid solution water content after concentrating is the 2%-50% of the initial water yield.
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Publication number Priority date Publication date Assignee Title
US5716895A (en) * 1993-04-01 1998-02-10 Nippon Kayaku Kabushiki Kaisha Process for regeneration of catalysts
CN1253131A (en) * 1998-10-29 2000-05-17 宝山钢铁(集团)公司 Process for preparing multiring or fused-ring binary carboxylate by heteropoly acid catalysis
CN1281749A (en) * 1999-07-22 2001-01-31 中国石油化工集团公司 Low timp. regeneration method of solid acid alkylation catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5716895A (en) * 1993-04-01 1998-02-10 Nippon Kayaku Kabushiki Kaisha Process for regeneration of catalysts
CN1253131A (en) * 1998-10-29 2000-05-17 宝山钢铁(集团)公司 Process for preparing multiring or fused-ring binary carboxylate by heteropoly acid catalysis
CN1281749A (en) * 1999-07-22 2001-01-31 中国石油化工集团公司 Low timp. regeneration method of solid acid alkylation catalyst

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