CN1532140A - Method for producing high purity yellow phosphrus - Google Patents
Method for producing high purity yellow phosphrus Download PDFInfo
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- CN1532140A CN1532140A CNA031175279A CN03117527A CN1532140A CN 1532140 A CN1532140 A CN 1532140A CN A031175279 A CNA031175279 A CN A031175279A CN 03117527 A CN03117527 A CN 03117527A CN 1532140 A CN1532140 A CN 1532140A
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- yellow phosphorus
- hno
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Abstract
The present invention relates to method of producing high purity yellow phosphorus. The production includes the following steps: decompression distilling industrial yellow phosphorus to eliminate mechanical impurity; reaction with concentrated sulfuric acid in condition of isolating air and washing with distilled water to eliminate residual sulfuric acid; reaction with HNO3 and oxidation reinforcer through stirring, washing with water solution of oxidant without pollution to phosphorus and washing with distilled water; and filtering with 2-5 micron filter to obtain yellow phosphorus in purity of 99.99-99.99999%. The said process has high product purity, operation safety and low cost and is suitable for use in industrial production.
Description
Technical field
The invention belongs to the production method of the production method of yellow phosphorus, particularly high-purity yellow phosphorus.
Technical background
At present, the technological line of yellow phosphorus purification has kind more than 20 approximately both at home and abroad, concludes to get up can be divided three classes: physics method, chemical method and other method.
The physics method has distillation, absorption, ion-exchange, extraction etc., and commonly used having distilled and extraction, but because phosphorus is similar to the arsenic behavior, is difficult to realize higher decreasing ratio; All contain inorganic impurity in the yellow phosphorus, absorption method is relatively poor to its separating effect; The ion exchange method security is relatively poor, and cost is also higher, realizes relatively difficulty of industrialization.
Chemical method is that mineral acid, alkali etc. is joined in the liquid phosphorus, makes impurity and its reaction, reaches the purpose of separating impurity.This method side reaction is many, and the phosphorus yield is low, poor stability.
Other method has Ah from new method, zone melting method, high temperature evaporation method etc.
Above-mentioned each method has the following disadvantages: all easily blast in implementation process (1), fire etc., has safety problem in various degree, and the technology of being developed is difficult to industrialization; (2) produce high-purity yellow phosphorus, it is impossible only depending on a kind of method, must just can obtain qualified product, yet this conscientiously not studied as yet at present with two or more method combinations; (3) still there is not the refining yellow phosphorus that a kind of method can be produced the different mass grade economically.
Summary of the invention
Technical problem to be solved by this invention provides a kind of production method of high-purity yellow phosphorus, its purification degree height, and operational safety is carried out suitability for industrialized production, cost for purification economy easily.
It is as follows to solve the scheme that technical problem of the present invention adopts:
(1), tentatively removes mechanical impurity, especially part metals impurity to the industrial yellow phosphorus underpressure distillation;
(2) under the secluding air situation,, remove remaining sulfuric acid with distilled water wash again with vitriol oil stirring reaction;
(3) and HNO
3With oxidation toughener stirring reaction, wash yellow phosphorus with hydrogen peroxide solution then, use distilled water wash again;
(4) strainer with 2 μ m～5 μ m filters, and obtains 99.99%～99.99999% yellow phosphorus.
In above-mentioned technical scheme, also should take following technique means: in the underpressure distillation operation to yellow phosphorus, temperature is controlled at 160 ℃～190 ℃, and vacuum tightness is adjusted according to distilled yellow phosphorus amount; With strong sulfuric acid response the time, the method for secluding air adopts nitrogen to protect, and temperature of reaction is 55 ℃～85 ℃, the concentration of the vitriol oil is 98%～150%, add-on is 5%～50% of a yellow phosphorus amount, and churning time is hour 0.5～1 hour, and washing is 10～15 times of yellow phosphorus amount with distilled water; With HNO
3The process of reaction, washing is carried out secondary, the HNO that this process is used first repeatedly
3Concentration is 20%, secondary HNO
3Concentration be stirring reaction time of 15%, twice all greater than 1 hour, the HNO of Jia Ruing first
3The volume of reaction solution is 3～4 times of yellow phosphorus volume, is for the second time 1～2 times of yellow phosphorus volume, and used hydrogen peroxide concentration is 3% during washing.
In order to obtain purer yellow phosphorus and to reduce cost, with HNO
3Reaction in used oxidation toughener through preferred, better with cetyl trimethylammonium bromide and ferric sulfate effect.When reacting first, should add the oxidation toughener; And when reacting for the second time, the oxidation toughener is only used cetyl trimethylammonium bromide, and looks concrete the addition that takes off assorted situation decision oxidation toughener, and the amount of resistates must add a small amount of more for a long time.For these reasons, what the vitriol oil should adopt is electronic-grade, and distilled water should reach GB/T6682-1992 standard, HNO
3, hydrogen peroxide, cetyl trimethylammonium bromide and ferric sulfate should adopt the analytical pure level.
Embodiment
Embodiment 1: take by weighing the industrial yellow phosphorus that the 2kg underpressure distillation obtains, put into the reactor of band bottom valve, chuck and an agitator with a certain amount of water, feed high pure nitrogen, water in the emptying reactor, extremely melt with 80 ℃ hot water yellow phosphorus in the reactor heating from chuck, and remove the less water that is dissolved in the yellow phosphorus, adding 300kg concentration is 105% the vitriol oil after stirring, again the hot water temperature is dropped to 60 ℃～70 ℃, 0.5 hour reaction times, after stopping to stir 5 minutes, bleed off all sulfuric acid in the reactor from bottom valve.After starting stirring, slowly add 15kg～20kg water (stopping logical nitrogen after adding 2kg water) from reactor top, remaining sulfuric acid is removed in washing.
The yellow phosphorus of above-mentioned processing is transferred to the reactor of a strap clamp cover and stirring system, 4 liters～6 liters in the nitric acid of adding concentration 20%, 0.2g cetyl trimethylammonium bromide and 5g～10g ferric sulfate, hot water reacting by heating liquid with 55 ℃～70 ℃, stirred 1 hour, use 3% hydrogen peroxide solution agitator treating then 2 hours, and be washed with distilled water to neutrality again.4 liters～6 liters in the nitric acid that in agitator, adds concentration 15% again, 0.1g cetyl trimethylammonium bromide with 55 ℃～70 ℃ hot water reacting by heating liquid, stirred 1 hour, use 3% hydrogen peroxide solution agitator treating then 2 hours, and be washed with distilled water to neutrality again.
The yellow phosphorus that the process previous step was handled, be frozen into fritter, strainer with 2 μ m～5 μ m in the hot aqueous medium carries out filtration under diminished pressure, the yellow phosphorus that obtains contains that As 0.8ppm, Fe 4.1ppm, Cu 0.3ppm, Zn 0.6ppm, organism (in C) 4.09ppm, S do not detect, Ni does not detect by analysis.
Embodiment 2: take by weighing the industrial yellow phosphorus that the 2kg underpressure distillation obtains, put into the reactor of band bottom valve, chuck and an agitator with a certain amount of water, feed high pure nitrogen, water in the emptying reactor, extremely melt with 80 ℃ hot water yellow phosphorus in the reactor heating from chuck, and remove the less water that is dissolved in the yellow phosphorus, adding 300kg concentration is 98% the vitriol oil after stirring, again the hot water temperature is dropped to 60 ℃～70 ℃, 0.5 hour reaction times, after stopping to stir 5 minutes, bleed off all sulfuric acid in the reactor from bottom valve.After starting stirring, slowly add 15kg～20kg water (stopping logical nitrogen after adding 2kg water) from reactor top, remaining sulfuric acid is removed in washing.
The yellow phosphorus of above-mentioned processing is transferred to the reactor of a strap clamp cover and stirring system, 4 liters～6 liters in the nitric acid of adding concentration 20%, 0.2g cetyl trimethylammonium bromide and 5g～10g ferric sulfate, hot water reacting by heating liquid with 55 ℃～70 ℃, stirred 1 hour, use 3% hydrogen peroxide solution agitator treating then 2 hours, and be washed with distilled water to neutrality again.In agitator, add 4 liters～6 liters in the nitric acid of concentration 15% again,, stirred 1 hour, used 3% hydrogen peroxide solution agitator treating then 2 hours, be washed with distilled water to neutrality again with 55 ℃～70 ℃ hot water reacting by heating liquid.
The yellow phosphorus that the process previous step was handled, be frozen into fritter, strainer with 2 μ m～5 μ m in the hot aqueous medium carries out filtration under diminished pressure, the yellow phosphorus that obtains contains that As 1ppm, Fe 3.1ppm, Cu 0.2ppm, Zn 0.7ppm, organism (in C) 4.9ppm, S do not detect, Ni does not detect by analysis.
Embodiment 3: take by weighing the industrial yellow phosphorus that the 2kg underpressure distillation obtains, put into the reactor of band bottom valve, chuck and an agitator with a certain amount of water, feed high pure nitrogen, water in the emptying reactor, extremely melt with 80 ℃ hot water yellow phosphorus in the reactor heating from chuck, and remove the less water that is dissolved in the yellow phosphorus, adding 300kg concentration is 120% the vitriol oil after stirring, again the hot water temperature is dropped to 60 ℃～70 ℃, 0.5 hour reaction times, after stopping to stir 5 minutes, bleed off all sulfuric acid in the reactor from bottom valve.After starting stirring, slowly add 15kg～20kg water (stopping logical nitrogen after adding 2kg water) from reactor top, remaining sulfuric acid is removed in washing.
The yellow phosphorus of above-mentioned processing is transferred to the reactor of a strap clamp cover and stirring system, 4 liters～6 liters in the nitric acid of adding concentration 20%, 0.2g cetyl trimethylammonium bromide and 5g～10g ferric sulfate, hot water reacting by heating liquid with 55 ℃～70 ℃, stirred 1 hour, use 3% hydrogen peroxide solution agitator treating then 2 hours, and be washed with distilled water to neutrality again.4 liters～6 liters in the nitric acid that in agitator, adds concentration 15% again, 0.1g cetyl trimethylammonium bromide with 55 ℃～70 ℃ hot water reacting by heating liquid, stirred 1 hour, use 3% hydrogen peroxide solution agitator treating then 2 hours, and be washed with distilled water to neutrality again.
The yellow phosphorus that the process previous step was handled, be frozen into fritter, strainer with 2 μ m～5 μ m in the hot aqueous medium filters filtration under diminished pressure, the yellow phosphorus that obtains contains that As 1.6ppm, Fe 3.1ppm, Cu 0.4ppm, Zn 0.7ppm, organism (in C) 3.8ppm, S do not detect, Ni does not detect by analysis.
Claims (4)
1, a kind of production method of high-purity yellow phosphorus is characterized in that step is as follows:
(1), tentatively removes mechanical impurity to the industrial yellow phosphorus underpressure distillation;
(2) under the secluding air situation,, remove remaining sulfuric acid with distilled water wash again with vitriol oil stirring reaction;
(3) and HNO
3With oxidation toughener stirring reaction, wash yellow phosphorus with hydrogen peroxide solution then, use distilled water wash again;
(4) strainer with 2 μ m～5 μ m filters, and obtains 99.99%～99.99999% yellow phosphorus.
2, by the production method of the described high-purity yellow phosphorus of claim 1, it is characterized in that:
(1) the distillatory service temperature is 160 ℃～190 ℃, and vacuum tightness is adjusted according to distilled yellow phosphorus amount;
Adopt the method for nitrogen protection to come secluding air during (2) with strong sulfuric acid response, temperature is 55 ℃～85 ℃, and the concentration of the vitriol oil is 98%～150%, and add-on is 5%～50% of a yellow phosphorus amount, churning time is hour 0.5～1 hour, and washing is 10～15 times of yellow phosphorus amount with distilled water;
(3) and HNO
3The process of reaction, washing is carried out secondary, HNO first
3Concentration be 20%, HNO for the second time
3Concentration be reaction times of 15%, twice all greater than 1 hour, HNO first
3The volume of reaction solution is 3～4 times of yellow phosphorus volume, is for the second time 1～2 times of yellow phosphorus volume, and washing is 3% with hydrogen peroxide concentration.
3, by the production method of the described high-purity yellow phosphorus of claim 2, it is characterized in that yellow phosphorus and HNO
3Reaction in used oxidation toughener be cetyl trimethylammonium bromide and ferric sulfate.
4, by the production method of the described high-purity yellow phosphorus of claim 2, what it is characterized in that vitriol oil employing is electronic-grade, and distilled water reaches GB/T6682-1992 standard, HNO
3, hydrogen peroxide, cetyl trimethylammonium bromide and ferric sulfate adopts the analytical pure level.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117527 CN1289388C (en) | 2003-03-20 | 2003-03-20 | Method for producing high purity yellow phosphrus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117527 CN1289388C (en) | 2003-03-20 | 2003-03-20 | Method for producing high purity yellow phosphrus |
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| Publication Number | Publication Date |
|---|---|
| CN1532140A true CN1532140A (en) | 2004-09-29 |
| CN1289388C CN1289388C (en) | 2006-12-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03117527 Expired - Fee Related CN1289388C (en) | 2003-03-20 | 2003-03-20 | Method for producing high purity yellow phosphrus |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759164B (en) * | 2009-12-09 | 2011-08-10 | 湖北兴福电子材料有限公司 | Production method of high-purity yellow phosphorus |
| CN103588185A (en) * | 2013-11-14 | 2014-02-19 | 云南江磷集团股份有限公司 | Method for removing sulfur from yellow phosphorus |
| CN109607501A (en) * | 2019-01-16 | 2019-04-12 | 中州新材料(杭州)有限公司 | A kind of purifying technique of yellow phosphorus |
| CN110078035A (en) * | 2019-05-07 | 2019-08-02 | 上海秦烯新材料科技有限公司 | A kind of method of sulphur in removal yellow phosphorus |
-
2003
- 2003-03-20 CN CN 03117527 patent/CN1289388C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759164B (en) * | 2009-12-09 | 2011-08-10 | 湖北兴福电子材料有限公司 | Production method of high-purity yellow phosphorus |
| CN103588185A (en) * | 2013-11-14 | 2014-02-19 | 云南江磷集团股份有限公司 | Method for removing sulfur from yellow phosphorus |
| CN103588185B (en) * | 2013-11-14 | 2016-03-02 | 云南江磷集团股份有限公司 | Yellow phosphorus sulfur method |
| CN109607501A (en) * | 2019-01-16 | 2019-04-12 | 中州新材料(杭州)有限公司 | A kind of purifying technique of yellow phosphorus |
| CN109607501B (en) * | 2019-01-16 | 2021-01-15 | 中州新材料(杭州)有限公司 | Yellow phosphorus purification process |
| CN110078035A (en) * | 2019-05-07 | 2019-08-02 | 上海秦烯新材料科技有限公司 | A kind of method of sulphur in removal yellow phosphorus |
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| Publication number | Publication date |
|---|---|
| CN1289388C (en) | 2006-12-13 |
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