CN103342346A - Preparation method of phosphine - Google Patents
Preparation method of phosphine Download PDFInfo
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- CN103342346A CN103342346A CN201310289015XA CN201310289015A CN103342346A CN 103342346 A CN103342346 A CN 103342346A CN 201310289015X A CN201310289015X A CN 201310289015XA CN 201310289015 A CN201310289015 A CN 201310289015A CN 103342346 A CN103342346 A CN 103342346A
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- phosphuret
- hydrogen
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- alcohol
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Abstract
The invention relates to a preparation method of phosphine. The preparation method comprises the following steps of: generating phosphine, hypophosphite and phosphite from yellow phosphorus under the action of a base, processing the hypophosphite and the phosphite by using an inorganic acid to obtain a mixture of hypophosphorous acid and phosphorous acid, and performing pyrolysis on the mixed acid to generate the phosphine and a byproduct, namely phosphoric acid. During the whole technological process of the preparation method, the byproducts, namely a sodium salt and the phosphoric acid are produced, the emission of wastes is reduced, and the yield of the phosphine is greatly improved by 50-68.3% in comparison with the highest yield of a traditional base method process.
Description
Technical field
The present invention relates to a kind of method of producing phosphuret-(t)ed hydrogen, relating in particular to a kind of is the method for feedstock production phosphuret-(t)ed hydrogen with yellow phosphorus.
Background technology
Phosphuret-(t)ed hydrogen is the important source material of industrial synthesis of alkyl phosphine, simultaneously, phosphuret-(t)ed hydrogen still is important N-type doped source in the semi-conductor industry, is used for multi crystal silicon chemical gaseous phase deposition, ion implantation technology and MOCVD technology etc., materials such as preparation extension gallium phosphide material, phosphorosilicate glass and passive film.Bottled phosphuret-(t)ed hydrogen and carbon dioxide gas mixture also just progressively replace aluminium phosphide becomes the grain depot fumigant.Phosphuret-(t)ed hydrogen mainly contains two kinds of explained hereafter industrial at present, and a kind of is acid technological process, and another kind is alkali process.Disproportionation generation phosphuret-(t)ed hydrogen and phosphoric acid take place in yellow phosphorus in the acid technological process in the acid effect and under up to 280 ℃ of temperature:
2P
4+12H
2O→5PH
3+3H
3PO
4
Yellow phosphorus disproportionation under the concentrated base effect generates phosphuret-(t)ed hydrogen and sodium hypophosphite and is attended by side reaction and generates sodium phosphite and hydrogen in the alkali process:
P
4+3H
2O+3NaOH→PH
3+3NaH
2PO
2
NaH
2PO
2+NaOH→Na
2HPO
3+H
2
The yield of acid technological process production phosphuret-(t)ed hydrogen and purity are all than alkali process height, but equipment requirements is very high.Have only U.S. cyanogen spy (Cytec, former American Cyanamid) company to produce phosphuret-(t)ed hydrogen (patent No. US3371994,1962) with acid technological process at present.The alkali process equipment requirements is lower, by other countries are adopted.But the phosphuret-(t)ed hydrogen yield of alkali process has only acid technological process half, is up to 30%.Corresponding by product sodium phosphite and sodium hypophosphite are more, are difficult to handle.This by product mainly is sodium phosphite and sodium hypophosphite mixture, is lower valency phosphorus, can further produce phosphuret-(t)ed hydrogen by pyrolysis.FMC Corp. utilizes sodium phosphite and sodium hypophosphite by product further to produce phosphuret-(t)ed hydrogen (patent No. US3116109,1961), and its method is to add phosphoric acid, pyrolysis gained mixture then in by product.This method increases the phosphuret-(t)ed hydrogen yield, but needs a large amount of phosphoric acid, increases production cost, and the processing of the after product of pyrolysis simultaneously also is a big problem.
Summary of the invention
The objective of the invention is in order to overcome the problem that existing explained hereafter phosphuret-(t)ed hydrogen exists, and a kind of yield height is provided, cost is low, waste discharge is few, is the method that starting raw material prepares phosphuret-(t)ed hydrogen with yellow phosphorus.
For achieving the above object, the invention provides a kind of preparation method of phosphuret-(t)ed hydrogen, be specially:
The low-carbon alcohol solvent of yellow phosphorus and C1-C5 is added in the reactor, with the interior air of nitrogen replacement reactor and keep stream of nitrogen gas, a little higher than normal atmosphere of pressure; Then reaction is warming up to 25 ℃-60 ℃, drips the sodium hydroxide solution of 20w/w%-60w/w% while stirring to reactor, treat that phosphuret-(t)ed hydrogen emits, continue to stir 4 hours-8 hours, pH is 8-12; Add mineral acid in reaction mixture, making mixture pH is 1-2; The low-carbon alcohol that adds C1-C3 then, stirred 0.5-1 hour down at 40 ℃-60 ℃, products therefrom is filtered, the a small amount of absolute ethanol washing of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid, and this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirs 2 hours-5 hours, emit up to no phosphuret-(t)ed hydrogen, resistates is phosphoric acid.
Method provided by the invention, the weight ratio of the low-carbon alcohol of yellow phosphorus and C1-C5 is 1: 5-20, as: but be not limited only to 1: 5,1: 6,1: 7,1: 8,1: 9,1: 10,1: 11,1: 12,1: 13,1: 14,1: 15,1: 16,1: 17,1: 18,1: 19 and 1: 20.
Method provided by the invention, the weight ratio of the sodium hydroxide solution of yellow phosphorus and 20w/w%-w/w60% is 1: 2-4, as: but be not limited only to 1: 2,1: 2.1,1: 2.2,1: 2.3,1: 2.4,1: 2.5,1: 2.6,1: 2.7,1: 2.8,1: 2.9,1: 3,1: 3.1,1: 3.2,1: 3.3,1: 3.4,1: 3.5,1: 3.6,1: 3.7,1: 3.8,1: 3.9 and 1: 4.
Method provided by the invention, the weight ratio of the low-carbon alcohol of yellow phosphorus and C1-C3 are 1: 5-10, as: but be not limited only to 1: 5,1: 5.5,1: 6,1: 6.5,1: 7,1: 7.5,1: 8,1: 8.5,1: 9,1: 9.5 and 1: 10.
The yield of phosphuret-(t)ed hydrogen is determined method: the phosphuret-(t)ed hydrogen of generation enters with stream of nitrogen gas and generates phosphorus mercury chloride precipitation in the absorption bottle of the mercuric chloride solution that concentration 2%-3% is housed.The growing amount of phosphuret-(t)ed hydrogen is determined by residue mercury chloride concentration and/or weight of precipitate.This method is based on the phosphuret-(t)ed hydrogen measuring method of generally acknowledging.
Term involved in the present invention is identical with its general concept.
Alleged " C " of the present invention is interpreted as carbon or carbon atom.Contained carbon atom and the quantity thereof of " C1-C5 " and " C1-C3 " expression, wherein letter C is represented carbon or carbon atom, numeral is positive integer thereafter, as: 1,2,3,4 or 5 etc., represent contained carbon or carbon atom number.Be the compound that C1 represents to contain 1 carbon atom, C3 represents to contain the compound of 3 carbon atoms, and " C1-C3 " expression contains 1 carbon atom to the one group of compound that contains 3 carbon atoms.Thus, those skilled in the art can understand the implication of other expression formula of above-mentioned and the similar type do not listed.
Alleged " low-carbon alcohol of C1-C5 " of the present invention comprises the unit alcohol of C1-C5, the dibasic alcohol of C2-C5 and the polyvalent alcohol of C3-C5, the preferential unit alcohol of selecting C1-C5, as: but be not limited only to methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and amylalcohol, these low-carbon alcohol are used separately or several mixing is used.
Mineral acid of the present invention, being interpreted as is that a class can dissociate hydrogen ion and not have other cationic mineral compound, its common form as: but be not limited only to hydrochloric acid, sulfuric acid and phosphoric acid etc., these mineral acids use separately or several mixing is used.
The present invention improves traditional phosphuret-(t)ed hydrogen reparation technology, yellow phosphorus is generated phosphuret-(t)ed hydrogen and recycling by product hypophosphite and phosphite under the alkali effect, get Hypophosporous Acid, 50 and phosphorous acid mixture with mineral acid treatment, the further pyrolysis of mixing acid is generated phosphuret-(t)ed hydrogen and by product phosphoric acid, increased substantially the phosphuret-(t)ed hydrogen yield, the highest yield than traditional alkali process has improved 50%-70%, reduced the consumption of raw material of producing phosphuret-(t)ed hydrogen, reduced the manufacturing cost of phosphuret-(t)ed hydrogen, used low-carbon alcohol can recycling use in the technology, wastage rate are low, separating mixture (being nitration mixture) is preferentially selected the low-carbon alcohol of C1-C3 for use, though other alcohols that can dissolve the higher carbon number of mixing acid also is suitable for, but it is uneconomical, whole technological process by product is sodium salt and phosphoric acid, all can be used as Chemicals uses, thereby the mixture of having avoided traditional technology to produce the by product of phosphuret-(t)ed hydrogen generation can't directly utilize, and can only be as the defective of waste treatment, reduced waste discharge, refuse is fully used, has reached not only environmental protection but also economic effect.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the invention is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
The used reagent of the present invention is not if clearly indicate, then all available from Sigma-aldrich (Sigma-Aldrich).
Embodiment 1
Yellow phosphorus 2.0g and methyl alcohol 20g are added in the reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas, a little higher than normal atmosphere of pressure; Be that 50% sodium hydroxide solution 4.0g slowly splashes in the reaction flask under 25 ℃ while stirring with mass percent concentration, slowly improve temperature to 60 ℃, the reaction solution color transfers reddish-brown to, phosphuret-(t)ed hydrogen is emitted, sodium hydroxide solution drips the back to be continued to stir 5 hours, reaction mixture becomes khaki color by reddish-brown, and pH is 9; Add the hydrochloric acid 5.2g of concentration 36%, making mixture pH is 2; Add dehydrated alcohol 15g, stirred 1 hour down at 50 ℃, get the liquid-solid body mixture of rice white; Solid mixture is filtered at normal temperatures, the a small amount of absolute ethanol washing of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid 2.8g, mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, heating and continuous 4 hours, emit phosphuret-(t)ed hydrogen yield 50.5% up to no phosphuret-(t)ed hydrogen.
Embodiment 2
Yellow phosphorus 2.0g and ethanol 20g are added in the reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas; Be that 50% sodium hydroxide solution 4.0g slowly splashes in the reaction flask under 25 ℃ while stirring with mass percent concentration, slowly improve temperature to 50 ℃, the reaction solution color transfers reddish-brown to, phosphuret-(t)ed hydrogen is emitted, sodium hydroxide solution drips the back to be continued to stir 4 hours, reaction mixture becomes khaki color by reddish-brown, and pH is 8; Add the sulfuric acid 2.6g of concentration 98%, making mixture pH is 1; Add Virahol 15g, stirred 0.5 hour down at 40 ℃, get the liquid-solid body mixture of rice white; Solid mixture is filtered at normal temperatures, a small amount of washed with isopropyl alcohol of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid 2.7g, this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirred 5 hours, and emitted phosphuret-(t)ed hydrogen yield 50% up to no phosphuret-(t)ed hydrogen.
Embodiment 3
Yellow phosphorus 2.0g and Virahol 20g are added in the reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas; Be that 50% sodium hydroxide solution 4.0g slowly splashes in the reaction flask under 30 ℃ while stirring with mass percent concentration, slowly improve temperature to 60 ℃, the reaction solution color transfers reddish-brown to, phosphuret-(t)ed hydrogen is emitted, sodium hydroxide solution drips the back to be continued to stir 6 hours, reaction mixture becomes khaki color by reddish-brown, and pH is 9; Add the phosphatase 24 .0g of concentration 85%, making mixture pH is 1; Add Virahol 15g, stirred 0.5 hour down at 50 ℃, get the liquid-solid body mixture of rice white; Solid mixture is filtered at normal temperatures, a small amount of washed with isopropyl alcohol of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid 3.0g, this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirred 2 hours, and emitted phosphuret-(t)ed hydrogen yield 47% up to no phosphuret-(t)ed hydrogen.
Embodiment 4
Yellow phosphorus 2.0g and butanols 10g are added in the reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas; Be that 50% sodium hydroxide solution 4.0g slowly splashes in the reaction flask under 30 ℃ while stirring with mass percent concentration, slowly improve temperature to 60 ℃, the reaction solution color transfers reddish-brown to, phosphuret-(t)ed hydrogen is emitted, sodium hydroxide solution drips the back to be continued to stir 6 hours, reaction mixture becomes khaki color by reddish-brown, and pH is 9; Add the hydrochloric acid 5.3g of concentration 36%, making mixture pH is 1; Add Virahol 10g, stirred 0.5 hour down at 50 ℃, get the liquid-solid body mixture of rice white; Solid mixture is filtered at normal temperatures, a small amount of washed with isopropyl alcohol of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid 2.9g, this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirred 2 hours, and emitted phosphuret-(t)ed hydrogen yield 45% up to no phosphuret-(t)ed hydrogen.
Embodiment 5
Yellow phosphorus 2.0g and amylalcohol 15g are added in the reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas; Be that 50% sodium hydroxide solution 8.0g slowly splashes in the reaction flask under 30 ℃ while stirring with mass percent concentration, slowly improve temperature to 60 ℃, the reaction solution color transfers reddish-brown to, phosphuret-(t)ed hydrogen is emitted, sodium hydroxide solution drips the back to be continued to stir 6 hours, reaction mixture becomes khaki color by reddish-brown, and pH is 12; Add the hydrochloric acid 10.4g of concentration 36%, making mixture pH is 1; Add Virahol 20g, stirred 1 hour down at 50 ℃, get the liquid-solid body mixture of rice white; Solid mixture is filtered at normal temperatures, the a small amount of washed with isopropyl alcohol of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid 3.1g, this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirred 2 hours, emit phosphuret-(t)ed hydrogen yield 50.5% up to no phosphuret-(t)ed hydrogen.
Embodiment 6
Yellow phosphorus 2.0g and methyl alcohol 20g are mixed with ethanol 20g in the back adding reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas; Be that 50% sodium hydroxide solution 6g slowly splashes in the reaction flask under 30 ℃ while stirring with mass percent concentration, slowly improve temperature to 60 ℃, the reaction solution color transfers reddish-brown to, phosphuret-(t)ed hydrogen is emitted, sodium hydroxide solution drips the back to be continued to stir 8 hours, reaction mixture becomes khaki color by reddish-brown, and pH is 11; Add the hydrochloric acid 7.6g of concentration 36%, making mixture pH is 1; Add ethanol 20g, stirred 1 hour down at 50 ℃, get the liquid-solid body mixture of rice white; Solid mixture is filtered at normal temperatures, and filter cake washs with small amount of ethanol, and filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid 3.2g, this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirred 2 hours, and emitted phosphuret-(t)ed hydrogen yield 48.5% up to no phosphuret-(t)ed hydrogen.
Comparing embodiment
Yellow phosphorus 2.0g and methyl alcohol 20g are added in the reaction flask, and the interior air of reaction flask is with nitrogen replacement and keep stream of nitrogen gas; Mass percent concentration is that 50% sodium hydroxide solution 4.0g slowly splashes under 25 ℃, slowly improves temperature to 50 ℃, and the reaction solution color transfers reddish-brown to, and phosphuret-(t)ed hydrogen is emitted; Sodium hydroxide solution drips the back and continued stirring reaction 4 hours, emits up to no phosphuret-(t)ed hydrogen, and reaction mixture is become slightly yellow by reddish-brown, and pH is 9; The hydrochloric acid 5.3g of adding 36%, making mixture pH is 1; Stirred 0.5 hour down at 60 ℃, moisture and methyl alcohol are removed in decompression, get little yellow solid mixture; This mixture is without isolating ortho phosphorous acid/phosphorous acid mixture, and direct heating to 200 ℃ phosphuret-(t)ed hydrogen generates, and pyrolysis continues 3 hours down at 200 ℃-250 ℃, emits phosphuret-(t)ed hydrogen yield 38.9% until no phosphuret-(t)ed hydrogen.
This shows that use in ortho phosphorous acid/phosphorous acid mixture process, separating step also has remarkably influenced to the phosphuret-(t)ed hydrogen yield.
Claims (7)
1. the preparation method of a phosphuret-(t)ed hydrogen is characterized in that the low-carbon alcohol solvent of yellow phosphorus and C1-C5 is added in the reactor, with the interior air of nitrogen replacement reactor and keep stream of nitrogen gas, a little higher than normal atmosphere of pressure; Then reaction is warming up to 25 ℃-60 ℃, slowly drips the sodium hydroxide solution of 20w/w%-60w/w% while stirring to reactor, treat that phosphuret-(t)ed hydrogen emits, continue to stir 4 hours-8 hours, pH is 8-12; Add mineral acid in described reaction mixture, making described mixture pH is 1-2; The low-carbon alcohol that adds C1-C3 then, stirred 0.5-1 hour down at 40 ℃-60 ℃, products therefrom is filtered, the a small amount of absolute ethanol washing of filter cake, filtrate decompression evaporate to dryness ethanol gets thick Hypophosporous Acid, 50 and phosphorous acid mixing acid, this mixing acid continues to emit phosphuret-(t)ed hydrogen 200 ℃ of-250 ℃ of following pyrolysis, stirs 2 hours-5 hours, emits up to no phosphuret-(t)ed hydrogen.
2. the preparation method of phosphuret-(t)ed hydrogen according to claim 1, the weight ratio that it is characterized in that the low-carbon alcohol of described yellow phosphorus and described C1-C5 is 1: 5-20.
3. the preparation method of phosphuret-(t)ed hydrogen according to claim 1, the weight ratio that it is characterized in that the sodium hydroxide solution of described yellow phosphorus and described 20w/w%-w/w60% is 1: 2-4.
4. the preparation method of phosphuret-(t)ed hydrogen according to claim 1, the weight ratio that it is characterized in that the low-carbon alcohol of described yellow phosphorus and described C1-C3 is 1: 5-10.
5. the preparation method of phosphuret-(t)ed hydrogen according to claim 1, the low-carbon alcohol that it is characterized in that described C1-C5 is selected from one or more of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and amylalcohol.
6. the preparation method of phosphuret-(t)ed hydrogen according to claim 1, the low-carbon alcohol that it is characterized in that described C1-C3 is selected from one or more of methyl alcohol, ethanol, propyl alcohol and Virahol.
7. the preparation method of phosphuret-(t)ed hydrogen according to claim 1 is characterized in that described mineral acid is selected from one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
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|---|---|---|---|
| CN201310289015XA CN103342346A (en) | 2013-07-10 | 2013-07-10 | Preparation method of phosphine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925774A (en) * | 2015-06-17 | 2015-09-23 | 上海正帆科技有限公司 | Electronic-grade phosphine synthesis and purification device and method |
| CN111348631A (en) * | 2018-12-21 | 2020-06-30 | 东泰高科装备科技有限公司 | Process for preparing phosphane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3116109A (en) * | 1961-03-10 | 1963-12-31 | Fmc Corp | Process for production of phosphine and phosphite-free phosphates |
| CN103253640A (en) * | 2012-12-07 | 2013-08-21 | 江苏先锋生物基技术研究中心有限公司 | Phosphine preparation method |
-
2013
- 2013-07-10 CN CN201310289015XA patent/CN103342346A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3116109A (en) * | 1961-03-10 | 1963-12-31 | Fmc Corp | Process for production of phosphine and phosphite-free phosphates |
| CN103253640A (en) * | 2012-12-07 | 2013-08-21 | 江苏先锋生物基技术研究中心有限公司 | Phosphine preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925774A (en) * | 2015-06-17 | 2015-09-23 | 上海正帆科技有限公司 | Electronic-grade phosphine synthesis and purification device and method |
| CN104925774B (en) * | 2015-06-17 | 2017-03-08 | 上海正帆科技有限公司 | A kind of synthesis of electron level phosphine and purifying plant and method |
| CN111348631A (en) * | 2018-12-21 | 2020-06-30 | 东泰高科装备科技有限公司 | Process for preparing phosphane |
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Application publication date: 20131009 |