CN108057439A - A kind of catalyst that hydrogen phosphide is catalytically decomposed and preparation method thereof - Google Patents

Abstract

A kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed, with the high titanium dioxide of chemical stability and thermal stability（TiO₂）For carrier, using aluminium isopropoxide, iron chloride as predecessor, nano-titanium dioxide is synthesized with sol-gal process（TiO₂）Then carrier is loaded using deposition-precipitation method, by the processes such as ultrasound, washing, dry, roasting, aluminium oxide is generated in carrier surface（Al₂O₃）, iron oxide（Fe₂O₃）Catalytic active center.It is an advantage of the invention that：Catalyst preparation process is simple and practicable, Fe₂O₃And Al₂O₃Load to TiO₂The photocatalytic activity of catalyst can be more improved on carrier, the catalytic decomposition efficiency of hydrogen phosphide can be greatly improved.

Description

A kind of catalyst that hydrogen phosphide is catalytically decomposed and preparation method thereof

Technical field

The present invention relates to the preparations that high poisonous gas phosphine catalyst is catalytically decomposed, particularly a kind of efficient doping metals oxygen The preparation method of compound catalyst.

Background technology

Hydrogen phosphide（PH₃）It is a kind of high poison, strong reducing property gas.Industrially, the production of a variety of phosphorus chemical products, semiconductor The processes such as the preparation of device and acetylene manufacture, can all generate PH₃Tail gas.At this stage, PH₃Vent gas treatment mainly has oxidizing process, inhales Attached method and combustion method, but these three methods can all generate secondary pollution, need further in increase economic efficiency etc. It improves.In recent years, PH₃Improvement yellow phosphorus is mainly prepared using catalytic decomposition method, wherein, the preparation and improvement of catalyst are One of important research contents, it is at present, positive on a variety of cobalts, ferroalloy and amorphous alloy catalyst, catalyst is born Suitable carrier is loaded in, not only contributes to the scattered of catalyst activity component, but also the activity of catalyst can be improved, using urging Change the method processing PH decomposed₃There are long-range and real environment and economic benefit.For this purpose, seek more catalytic effects it is good and The cheap catalyst being easy to get has vast potential for future development.

The content of the invention

The main treating method of hydrogen phosphide is generated the purpose of the present invention is being directed to current chemical industry, one kind is provided and is efficiently mixed The preparation method of miscellaneous metal oxide catalyst, the preparation method reaction condition is mild, simple for process, and gained catalyst simultaneously can Efficient catalytic decomposing phosphine.

Technical scheme.

A kind of preparation method that phosphine catalyst is catalytically decomposed, with the high titanium dioxide of chemical stability and thermal stability Titanium（TiO₂）For carrier, using aluminium isopropoxide, iron chloride as predecessor, nano-titanium dioxide is synthesized with sol-gal process（TiO₂）It carries Then body is loaded using deposition-precipitation method, by the processes such as ultrasound, washing, dry, roasting, generate and aoxidize in carrier surface Aluminium（Al₂O₃）, iron oxide（Fe₂O₃）Catalytic active center specifically comprises the following steps：1）Matched somebody with somebody with butyl titanate, water, ethyl alcohol Put TiO₂Colloidal sol is 4 with nitric acid adjustment pH；2）It is mixed with aluminium isopropoxide and water, enriching nitric acid adjustment pH values are 3, water-bath Certain time obtains Al₂O₃Colloidal sol；3）By 1）With 2）It is mixed in a certain ratio the Al for uniformly, obtaining different ratio₂O₃-TiO₂It is multiple Close colloidal sol；4）Appropriate iron chloride is taken to be dissolved in distilled water, adds in appropriate 3）The complex sol of middle preparation adds a certain amount of Sodium citrate, mixing ultrasound add in sodium carbonate liquor, and adjustment pH value is 8；5）By 4）It filters, washs, dry, what is obtained is dry solidifying Glue grind into powder is fired to be made loaded catalyst Al₂O₃-Fe₂O₃/TiO₂。

The carrier of the catalyst is titanium dioxide（TiO₂）, wherein TiO₂For Detitanium-ore-type.

The catalytic active center ingredient is Al₂O₃-Fe₂O₃。

The catalytic active center ingredient is Al₂O₃-Fe₂O₃, wherein Al₂O₃Content is 0.1%~10%, Fe₂O₃Content be 0.1%~5%.

It is an advantage of the invention that：TiO₂Structure, property are stablized, and are common excellent catalysts in a kind of air, water process, By Fe₂O₃Load to TiO₂Than single TiO on carrier₂Carrier can more improve activity, the selectivity of catalyst, and catalyst is made to exist Low temperature active, high temperature reducibility, anti-toxicity, etc. it is outstanding；Research shows in TiO₂Three kinds of crystal phase structures in, With anatase TiO₂Photocatalytic activity highest, Al₂O₃Doping can effectively inhibit TiO₂Turn from Anatase to Rutile Type Become, and then improve anatase TiO₂Crystallization, Al₂O₃Incorporation improve TiO to a certain extent₂Photocatalytic activity, can To greatly improve the catalytic decomposition efficiency of hydrogen phosphide.

Specific embodiment

With reference to embodiment, the present invention is further described, but they are not that the present invention is imposed any restrictions.This In only point out, the reagent that uses and test equipment are the commercially available universal product in addition to especially indicating the source in the present invention.

Embodiment 1.

A kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed, includes the following steps：1）With butyl titanate, water, Ethyl alcohol（Molar ratio is 1/10/0.25）Configure TiO₂Colloidal sol is 4 with nitric acid adjustment pH value；2）With aluminium isopropoxide and water（Molar ratio 1/100）1h is mixed, enriching nitric acid adjustment pH values are 3,80 DEG C of water-baths 24 h of reflux, obtain Al₂O₃Colloidal sol；3）By 1）With 2）By Al₂O₃Account for Al₂O₃/TiO₂The molar content of compound total amount be respectively 5%, 10%, 20%, 30%, 40% ratio mixing it is equal It is even, obtain the TiO of different ratio₂-Al₂O₃Complex sol;4）By 1.5g iron chloride solution in 200 mL distilled water, add in appropriate 3）The complex sol of middle preparation adds a certain amount of sodium citrate, mixes ultrasound 1 h, 80 DEG C of stirring in water bath 26h, adds dropwise Enter sodium carbonate liquor, adjustment pH value is 8；5）By 4）It filters, washs, dry, obtained xerogel grind into powder, through 400 DEG C 6h is roasted to get loaded catalyst Al₂O₃-Fe₂O₃/TiO₂, wherein Al₂O₃Content is 0.8%, Fe₂O₃Content be 0.5%.

By gained catalyst for phosphine gas catalytic decomposition experiment, to contain PH₃Molal quantity is 1% PH₃/N₂Gaseous mixture For reaction gas, gas space velocity is 2520 mL/ (h gcat), under 365 nm ultraviolet radiations, to PH at a temperature of 400 DEG C₃ Resolution ratio reach 75.0%.

Embodiment 2.

A kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed, includes the following steps：1）With butyl titanate, water, Ethyl alcohol（Molar ratio is 1/5/0.25）Configure TiO₂Colloidal sol is 4 with nitric acid adjustment pH value；2）With aluminium isopropoxide and water（Molar ratio 1/50）1 h is mixed, enriching nitric acid adjustment pH values are 3,80 DEG C of water-baths 24 h of reflux, obtain Al₂O₃Colloidal sol；3）By 1）With 2）By Al₂O₃Account for Al₂O₃/TiO₂The molar content of compound total amount be respectively 5%, 10%, 20%, 30%, 40% ratio mixing it is equal It is even, obtain the TiO of different ratio₂-Al₂O₃Complex sol；4）By 2.0 g iron chloride solutions in 200 mL distilled water, add in appropriate 3）The complex sol of middle preparation adds a certain amount of sodium citrate, mixes ultrasound 1 h, 80 DEG C of 26 h of stirring in water bath, adds dropwise Enter sodium carbonate liquor, adjustment pH value is 8；5）By 4）It filters, washs, dry, obtained xerogel grind into powder, through 400 DEG C 6 h are roasted to get loaded catalyst Al₂O₃-Fe₂O₃/TiO₂, wherein Al₂O₃Content is 0.6%, Fe₂O₃Content be 0.8%.

Embodiment 3.

A kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed, includes the following steps：1）With butyl titanate, water, Ethyl alcohol（Molar ratio is 1/10/0.25）Configure TiO₂Colloidal sol is 4 with nitric acid adjustment pH value；2）With aluminium isopropoxide and water（Molar ratio 1/50）1 h is mixed, enriching nitric acid adjustment pH values are 3,80 DEG C of water-baths 24 h of reflux, obtain Al₂O₃Colloidal sol；3）By 1）With 2）By Al₂O₃Account for Al₂O₃/TiO₂The molar content of compound total amount be respectively 5%, 10%, 20%, 30%, 40% ratio mixing it is equal It is even, obtain the TiO of different ratio₂-Al₂O₃Complex sol；4）By 1.0 g iron chloride solutions in 100 mL distilled water, add in appropriate 3）The complex sol of middle preparation adds a certain amount of sodium citrate, mixes ultrasound 1 h, 80 DEG C of 26 h of stirring in water bath, adds dropwise Enter sodium carbonate liquor, adjustment pH value is 8；5）By 4）It filters, washs, dry, obtained xerogel grind into powder, through 400 DEG C 6 h are roasted to get loaded catalyst Al₂O₃-Fe₂O₃/TiO₂, wherein Al₂O₃Content is 0.5%, Fe₂O₃Content be 0.9%.

By gained catalyst for phosphine gas catalytic decomposition experiment, to contain PH₃Molal quantity is 1% PH₃/N₂Gaseous mixture For reaction gas, gas space velocity is 2520 mL/ (h gcat), under 365nm ultraviolet radiations, to PH at a temperature of 450 DEG C₃ Resolution ratio reach 84.8%.

The present invention discloses a kind of preparation method of efficient catalytic decomposing phosphine catalyst, and those skilled in the art can pass through Use for reference present disclosure, the appropriate links such as process route that change are realized, although the method for the present invention by preferred embodiment into Description is gone, related technical personnel can substantially be modified method described herein not departing from present invention and scope Or reconfigure, to realize final result.In particular, it should be pointed out that all similar replacements and change are to art technology It is it will be apparent that they are considered as being included in present disclosure and scope for personnel.

Claims (5)

1. a kind of preparation method that phosphine catalyst is catalytically decomposed, with the high titanium dioxide of chemical stability and thermal stability （TiO₂）For carrier, using aluminium isopropoxide, iron chloride as predecessor, nano-titanium dioxide is synthesized with sol-gal process（TiO₂）Carrier, Then using deposition-precipitation method load, by the processes such as ultrasound, washing, dry, roasting, aluminium oxide is generated in carrier surface （Al₂O₃）, iron oxide（Fe₂O₃）Catalytic active center specifically comprises the following steps：1）With butyl titanate, water, ethyl alcohol（Mole Than for：1/1~10/0.25）Configure TiO₂Colloidal sol is 4 with nitric acid adjustment pH value；2）With aluminium isopropoxide and water（Molar ratio 1/20 ~100）1h is mixed, enriching nitric acid adjustment pH value for 24 hours, obtains Al for 3,80 DEG C of water-bath reflux₂O₃Colloidal sol；3）By 1）With 2） By Al₂O₃Account for Al₂O₃/TiO₂The molar content of compound total amount is respectively that 5%, 10%, 20%, 30%, 40% ratio is uniformly mixed, Obtain the TiO of different ratio₂-Al₂O₃Complex sol；4）By 1.5 g iron chloride solutions in 200 mL distilled water, appropriate 3 are added in） The complex sol of middle preparation, adds a certain amount of sodium citrate, mixing ultrasound 1h, and 80 DEG C of 26 h of stirring in water bath are added dropwise Sodium carbonate liquor, adjustment pH value are 8；5）By 4）It filters, washs, dry, obtained xerogel grind into powder, through 400 DEG C of roastings 6 h are burnt to get loaded catalyst Al₂O₃-Fe₂O₃/TiO₂, the wherein content of titanium dioxide is 0.1%~50%, and aluminium oxide contains It measures as 0.1%~10%, the content of iron oxide is 0.1%~10%.

2. a kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed according to claim 1, it is characterised in that：It is described to urge The activated centre of agent is Al₂O₃-Fe₂O₃。

3. a kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed according to claim 1, it is characterised in that：It is described to urge Agent has scattered activity well.

4. a kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed according to claim 1, it is characterised in that：It is described to urge Agent has the function of that hydrogen phosphide is catalytically decomposed.

5. a kind of preparation method for the catalyst that hydrogen phosphide is catalytically decomposed according to claim 1, it is characterised in that：It is described to urge The content of titanium dioxide is 0.1%~50% in agent, and the content of aluminium oxide is 0.1%~10%, the content of iron oxide for 0.1%~ 10%。