CN1264619A - Process for preparing supermicro particles of vanadium phosphorus oxide and its products - Google Patents
Process for preparing supermicro particles of vanadium phosphorus oxide and its products Download PDFInfo
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- CN1264619A CN1264619A CN 99114080 CN99114080A CN1264619A CN 1264619 A CN1264619 A CN 1264619A CN 99114080 CN99114080 CN 99114080 CN 99114080 A CN99114080 A CN 99114080A CN 1264619 A CN1264619 A CN 1264619A
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Abstract
a process for preparing supermicro particles of vanadium phosphorus oxide includes reaction between V2O5, hydrochloric acid and phosphoric acid, adding citric acid, evaporating over water both until it becomes gel, exchange with absulute alcohol, supercritical fluid drying in alcohol medium, and activating. Obtained supermicro particles have 30-200 nm of granularity and 7-176 sq.m./g of specific surface. The oxidized surface vanadium is +4 valence.
Description
The present invention relates to vanadium phosphorus oxide, specifically, relate to the preparation method and the goods thereof of supermicro particles of vanadium phosphorus oxide.
The VPO compounds is usually used in carbon four hydrocarbon (normal butane, butylene) oxidation system MALEIC ANHYDRIDE catalyst for reaction, and this process is to realize that by heterogeneous catalyst business-like alkane selective oxidation reaction is [referring to G.Emig, F.Martin, Catal.Today, 1,477 (1987)].With adopting benzene is that the old operational path of raw material is compared, the more difficult oxidation of butane, and reaction conditions is relatively harsher, yield of maleic anhydride lower [referring to J.Ebner, V.Franchetti, G.Centi, F.Trifiro, Chem.Rev., 88,251 (1988)].Therefore the modification to catalyzer is the focus that people pay close attention to always.So far, the most effective catalyzer of this catalytic process is vanadium phosphorus oxygen compounds [referring to G.Centi, Catal.Today, 16,5 (1993)].In recent years, worldwide, " Green Chemistry " was surging forward, and required the chemical reaction of " atom economy " and " zero release " to produce [referring to Min Enze, chemical progress, 10 (2), 207 (1998)].Therefore improve the selectivity that butane is converted into cis-butenedioic anhydride and not only have important economic value, and significant for environment protection.U.S. Dupont company once adopted riser reactor, all or part of lattice oxygen oxidation that utilizes catalyzer.It is said the selectivity [R.M.Contracor, H.E.Bergna, H.S.Horowitz etal., Catal.Today, 1,49 (1987)] that can improve reaction significantly.The inspiration that obtains thus is, if can improve the catalyst surface lattice oxygen capacity and the further reactivity of modulation lattice oxygen, and then adopting the lattice oxygen oxidation will be very favourable to further raising selectivity.In addition, improve the lattice surface oxygen capacity and can also reduce the circulation of catalyzer and the required energy consumption that circulates.And improve one of effective way of lattice surface oxygen capacity, be the ultramicron of vanadium phosphorus oxide being made bigger serface.
So far, though the research a lot [referring to B.K.Hodnett, Catal.Rev.-Sci.Eng., 27,373 (1985)] of preparation vanadium composite phosphorus oxide, chemical preparation ultramicron vanadium phosphorus oxidation compound yet there are no reported in literature.The system thinking of this prepared in laboratory chemistry also shows, existing traditional preparation method or conventional colloidal sol～gel method, and the vanadium phosphorus oxygen composite oxide particle that makes is bigger, is micron order, and the particle size dispersion inequality, and specific surface area is less, generally 2～20
2M/g.This is to be determined by the character of vanadium phosphorus oxygen compounds itself and characteristics.
By the method [referring to K.Shima, M.Ito, M.Murayama and M.Hatano, Sci.Tech.Catal.1994, Kodansha, Tokoy, 1995, P355.] of physical grinding, though particle diameter is reduced, specific surface area increases (＜40
2M/g), but not easy to operate when producing in enormous quantities, the collection of sample is difficulty relatively, and the poor repeatability of preparation.
The purpose of this invention is to provide and a kind ofly directly prepare the method for supermicro particles of vanadium phosphorus oxide simply with chemical process, a further object of the present invention provides the supermicro particles of vanadium phosphorus oxide that makes with the inventive method.
Technical scheme of the present invention is as follows:
A kind of preparation method of supermicro particles of vanadium phosphorus oxide, it is with V
2O
5, hydrochloric acid or hydroxylamine hydrochloride, and phosphoric acid one react, the reaction back that finishes adds citric acid, also can add auxiliary agent simultaneously, as ZrOCl
2(NH
4)
6Mo
7O
24, evaporate in the water-bath, to gel, handle with the dehydrated alcohol exchange again, in ethanol medium, carry out supercritical fluid drying then, high-temperature activation in air or nitrogen or reaction mixture gas promptly gets supermicro particles of vanadium phosphorus oxide at last.
Aforesaid method is described, and to carry out supercritical fluid drying in ethanol medium be in ethanol medium, at 240～280 ℃, and the supercritical fluid drying that carries out under 7.5～9.0MPa pressure.The described reaction mixture gas of aforesaid method is the gas mixture of normal butane, oxygen and nitrogen.The supermicro particles of vanadium phosphorus oxide that makes with the inventive method is that the atomic ratio of vanadium and phosphorus is 1.0: 1.1～1.2.Particle diameter is 30～200nm, and specific surface area is 17～176
2M/g.
If when adding citric acid, add auxiliary agent ZrOCl
2(NH
4)
6Mo
7O
24The atomic ratio of the supermicro particles of vanadium phosphorus oxide vanadium that then makes, phosphorus, zirconium, molybdenum is:
1.0: 1.1～1.2: 0.13～0.14: 0.0085～0.0086, particle diameter is 30～200nm, specific surface area is 17～176
2M/g.
The preparation method of supermicro particles of vanadium phosphorus oxide of the present invention is simple, can directly make ultramicron.Measure through TEM, particle diameter is 30～200nm, and measuring its specific surface area through BET is 17～176m
2/ g.The ultramicron particle diameter of gained is even.XRD determining, particle both may be non-crystalline states, also may be crystal form, a kind of unknown material phase that its crystalline phase and the relevant vanadium phosphorus oxygen composite oxide and all kinds of intermediate of bibliographical information all do not match.XPS measures and shows that the oxidation state of surperficial vanadium is essentially+4 valencys, is similar to the surperficial vanadium in the Vanadyl pyrophosphate.
By the following examples, further specify the present invention.
Embodiment one: with 18g V
2O
5Place flask, add the dense HCl of 167ml, refluxed 1.5 hours.Add again and determine that metering is than required 85%H
3PO
4, be 16ml herein, the P/V atomic ratio is 1.2: 1.And refluxed 1.5 hours.After the cooling, add the aqueous solution 120ml that contains citric acid 30g, in the water-bath about 80 ℃, be evaporated to gel.Handle for several times and remove alcohol solvent with the dehydrated alcohol exchange.In the 280ml anhydrous ethanol medium, 260 ℃, supercritical fluid drying in the autoclave, pressure are about 8.5MPa.Snap-out release alcohol vapour and in high-purity N
2Protection is cooling down, gained sample 400 ℃ of calcination activations 6 hours in air atmosphere, final sample.Specific surface area: 56
2M/g, size of particles :～50nm.Crystallization phases is arranged.If at reaction mixture gas (1.5%n-C
4H
10+ 17%O
2+ N
2Equal amount, down with) in activation 6 hours, the sample specific surface area is 56
2M/g, particle begin to occur microcrystallite less than 50nm.Prolong soak time to 24 hour in reaction mixture gas, specific surface area is 48
2M/g, particle have increase slightly, but still less than 100nm, and still be microcrystalline state.At N
2Activation is 6 hours in the gas mixture, and specific surface area is 72
2M/g, particle are less than 50nm, and crystal grain is very little, crystallization a little less than.Sample activates in different atmosphere, and its size of particles all distributes evenly.The oxidation state of surface V all approaches+4 valencys.
Embodiment two: with 12gV
2O
5Place flask, add the dense HCl of 111ml, refluxed 1.5 hours.Add again and determine that metering is than required 85%H
3PO
4(be 10.67ml, P: the V atomic ratio is 1.2: 1 herein).Continue to reflux 1.5 hours.After the cooling, add the 150ml aqueous solution that contains citric acid 30g, and add 2.6g ZrOCl
26H
2O (one of auxiliary agent), 0.7g (NH
4)
6Mo
7O
244H
2O (auxiliary agent two) is evaporated to gel in 80 ℃ of water-baths.In the 260ml anhydrous ethanol medium, 265 ℃, supercritical fluid drying in the autoclave, pressure are about 8.0MPa.The gained sample activates 6 hours in gas mixture, specific surface area: 67
2M/g, particle diameter is less than 40nm.Basically be noncrystalline state, activation is 24 hours in the reaction mixture gas, and specific surface area is 47
2M/g, particle is partly reunited, and sample has crystallization slightly.
If at N
2Middle activation 6 hours, specific surface area: 176
2M/g, particle diameter be less than 40nm, noncrystalline state.When activating in the different atmosphere, size of particles all distributes evenly.The surface vanadium oxidation state approaching+4 valencys.
Embodiment three: with 16m 185%H
3PO
4, 13.9g NH
2OHHCl and 200ml distilled water are mixed into solution.At 80 ℃, add 18.2g V
2O
5, under this temperature, stir, be evaporated to the formation gel.Handle for several times and remove alcohol solvent with dehydrated alcohol.In the 280ml anhydrous ethanol medium, 262 ℃, supercritical fluid drying in the autoclave, pressure are about 7.5MPa again, snap-out release alcohol vapour and in high-purity N
2Protection is cooling down, the 400 ℃ of activation 6 hours in air atmosphere of gained sample, specific surface area: 17
2M/g, size of particles :～200nm.Greater than nanoscale, but be ultrafine particle.If activation is 6 hours in reaction mixture gas, specific surface area: 17
2M/g, size of particles: 160～200nm unknown material phase.
Activation is 24 hours in reaction mixture gas, specific surface area: 17
2M/g, size of particles: about 200nm, the unknown material phase.
At N
2Middle activation 6 hours, specific surface area: 20m
2/ g, size of particles :～200nm, unknown material phase.When activating in the different gas mixtures, particle size distribution is even.
Claims (7)
1. the preparation method of a supermicro particles of vanadium phosphorus oxide is characterized in that V
2O
5, hydrochloric acid or NH
2OHHCl, phosphoric acid one react, after finishing, reaction adds citric acid, evaporate in the water-bath, to gel, handle with the dehydrated alcohol exchange again, carry out supercritical fluid drying then in ethanol medium, high-temperature activation in air or nitrogen or reaction mixture gas promptly gets supermicro particles of vanadium phosphorus oxide at last.
2. preparation method according to claim 1 is characterized in that adding citric acid after reaction finishes, and adds auxiliary agent simultaneously.
3. preparation method according to claim 1 is characterized in that adding auxiliary agent after reaction finishes is ZrOCl
2(NH
4)
6Mo
7O
24
4. preparation method according to claim 1 and 2 is characterized in that in ethanol medium, at 240～280 ℃, carries out supercritical fluid drying under 7.5～9.0MPa pressure.
5. preparation method according to claim 1 and 2 is characterized in that reaction mixture gas is a normal butane, the gas mixture of oxygen and nitrogen.
6. the supermicro particles of vanadium phosphorus oxide of preparation according to claim 1, the atomic ratio that it is characterized in that vanadium and phosphorus is 1.0: 1.1～1.2, and particle diameter is 30～200nm, and specific surface area is 17～176
2M/g.
7. the supermicro particles of vanadium phosphorus oxide of method preparation according to claim 2, the atomic ratio that it is characterized in that vanadium, phosphorus, zirconium, molybdenum is 1.0: 1.1～1.2: 0.13～0.14: 0.0085～0.0086, and particle diameter is 30～200nm, and more long-pending than performance is 17～176m
2/ g.
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|---|---|---|---|
| CNB99114080XA CN1181920C (en) | 1999-02-26 | 1999-02-26 | Process for preparing supermicro particles of vanadium phosphorus oxide and its products |
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|---|---|---|---|
| CNB99114080XA CN1181920C (en) | 1999-02-26 | 1999-02-26 | Process for preparing supermicro particles of vanadium phosphorus oxide and its products |
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|---|---|
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| CN1181920C CN1181920C (en) | 2004-12-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769183A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide, and preparation method thereof |
| CN103769181A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vanadium-phosphorus-oxygen catalyst, and preparation method thereof |
| CN104549394A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide catalyst and preparation method thereof |
| CN104549393B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide and preparation method thereof |
-
1999
- 1999-02-26 CN CNB99114080XA patent/CN1181920C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769183A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide, and preparation method thereof |
| CN103769181A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vanadium-phosphorus-oxygen catalyst, and preparation method thereof |
| CN104549394A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide catalyst and preparation method thereof |
| CN104549394B (en) * | 2013-10-22 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of vanadium-phosphor oxide catalyst and preparation method thereof |
| CN104549393B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1181920C (en) | 2004-12-29 |
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Granted publication date: 20041229 |