CN106853959A - A kind of method that use impure selenium wet method prepares high purity selenium - Google Patents
A kind of method that use impure selenium wet method prepares high purity selenium Download PDFInfo
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- CN106853959A CN106853959A CN201610827749.2A CN201610827749A CN106853959A CN 106853959 A CN106853959 A CN 106853959A CN 201610827749 A CN201610827749 A CN 201610827749A CN 106853959 A CN106853959 A CN 106853959A
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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Abstract
The invention discloses a kind of method that use impure selenium wet purification prepares high purity selenium, its step is：A, impure selenium is slowly at the uniform velocity added in sodium hydroxide solution, the solid mass ratio of liquid is 3 ~ 5:1, the reaction time is 1.5 ~ 2h, it is ensured that impure selenium is completely dissolved leaching；B, with salt acid for adjusting pH to 6.5 ~ 7.0, add vulcanized sodium, stir and evenly mix, stand removal of impurities；C, alkali immersion liquid are continued to adjust pH to 1.0 ~ 1.5 with hydrochloric acid, are aged 2.5 ~ 3h, and selenium precipitation is complete, separation of solid and liquid；D, with sodium sulfite solution Oxidation Leaching essence selenium, be sufficiently stirred for, selenium-rich liquid is filtered to obtain after standing；E, toward sulfuric acid is slowly added in selenium-rich liquid, acidifying reduction, filtering, washing is dried, and high purity selenium is obtained.The present invention realizes two steps and leaches wet purification impure selenium preparation high purity selenium, shortens selenium purifying flow, improves the rate of recovery, reduces production cost, reduces the limitation of large-scale production.
Description
Technical field
Field is produced the present invention relates to high-purity rare metal, and in particular to a kind of use impure selenium wet purification prepares high
The process of purity selenium.
Background technology
At present, the main of external production high purity selenium has Germany, Chile, Japan etc., but its purifying technique key technology
Strict secrecy is carried out, it is difficult to find relevant report from the document published.The technique of country's purification selenium is mainly aerobic
Change-adsorption precipitation method, neutralization-hydrolysis combined method, ion exchange-extraction, these methods exist technological process long, high cost,
The low problem of the seriously polluted, rate of recovery is difficult to mass produce.Chinese patent application CN102627262 (application numbers
201210129139.7) " method that high purity selenium is extracted from the byproduct of high temperature scarlet color production " discloses a kind of from high temperature
The method that high purity selenium is extracted in the byproduct of large red production, mainly for the parcel waste material in ceramic industry, excludes and selenium
The chaff interferences such as silicon, zirconium, cadmium, sulphur that cadmium coexists, extract high-purity selenium, and preparing high purity selenium with impure selenium wet purification does not have general character.
《The purifying and preparation of high-purity selenium》（Investigation of materials and application, Wu Hao etc., Vol.4, No.4, Dec.2010）In disclose a kind of logical
The purifying technique that peroxidating burning-vacuum distillation is combined, raw material is 99.9% selenium, has no and carried for 80-90% miscellaneous impure seleniums high
Pure technique.
Therefore it provides a kind of preparation method of new preparation high purity selenium, is a good problem to study.
The content of the invention
In order to overcome above-mentioned deficiency of the prior art, the present invention to provide a kind of Whote-wet method technique leached using two steps,
Remove impurity, the method for purifying and preparing high-purity selenium.
The object of the present invention is achieved like this：
A kind of method that use impure selenium wet purification prepares high purity selenium, it is characterised in that comprise the following steps：
A, impure selenium is first used into water slurry, use the mode of slurry type feeding to be slowly at the uniform velocity added to the hydrogen that mass fraction is for 35% ~ 50%
In sodium hydroxide solution, it is 3 ~ 5 to control the solid mass ratio of liquid:1, extraction time is 1.5 ~ 2h, it is ensured that impure selenium is completely dissolved leaching；
B, the hydrochloric acid regulation alkali immersion liquid pH to 6.5 ~ 7.0 with mass fraction 5 ~ 20%, add the vulcanization of 0.5 ~ 2 times of impure selenium dry weight
Sodium, stirs and evenly mixs, and stands 1h filtering and impurity removings；
C, alkali immersion liquid continue to adjust pH to 1.0 ~ 1.5 with the hydrochloric acid of mass fraction 10% ~ 30%, are aged 2.5 ~ 3h, take supernatant inspection
Survey Se content in solution（≤0.15g/l）, completely, separation of solid and liquid obtains smart selenium to selenium precipitation；
D, the sodium sulfite solution Oxidation Leaching essence selenium with mass fraction 40% ~ 50%, it is 2 ~ 4 to control the solid mass ratio of liquid:1, leach
75 ~ 100 DEG C of temperature, extraction time is 2 ~ 4h, is then filtrated to get selenium-rich liquid；
E, toward the hot dilute sulfuric acid that 5 ~ 200g/l is slowly added in selenium-rich liquid, acidifying reduction, water-bath is incubated 2 ~ 3h, filtering, washing, dry
It is dry, high purity selenium is obtained.
In step a, selenium water quality ratio is 1 ~ 2 in slurry type feeding:2；
In step c, the method for Se content is in detection supernatant：The supernatant after the heavy selenium of 5ml is taken, the KI of 1ml is instilled
（10g/l）Blueness is occurred without, i.e. selenium precipitation is complete；
In step d, extraction temperature is 75 ~ 100 DEG C；
In step e, selenium precipitation is washed with the ethanol solution that volume fraction is 50%.
Positive beneficial effect：The present invention realizes two steps and leaches wet purification impure selenium preparation high purity selenium, shortens selenium pure
Change flow, improve the rate of recovery, reduce production cost, reduce the limitation of large-scale production.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but protection scope of the present invention not limited to this.
As shown in figure 1, a kind of method that use impure selenium wet purification prepares high purity selenium, it is characterised in that including following
Step：
A, impure selenium is first used into water slurry, use the mode of slurry type feeding to be slowly at the uniform velocity added to the hydrogen that mass fraction is for 35% ~ 50%
In sodium hydroxide solution, it is 3 ~ 5 to control the solid mass ratio of liquid:1, extraction time is 1.5 ~ 2h, it is ensured that impure selenium is completely dissolved leaching；
B, the hydrochloric acid regulation alkali immersion liquid pH to 6.5 ~ 7.0 with mass fraction 5 ~ 20%, add the vulcanization of 0.5 ~ 2 times of impure selenium dry weight
Sodium, stirs and evenly mixs, and stands 1h filtering and impurity removings；
C, alkali immersion liquid continue to adjust pH to 1.0 ~ 1.5 with the hydrochloric acid of mass fraction 10% ~ 30%, are aged 2.5 ~ 3h, take supernatant inspection
Survey Se content in solution（≤0.15g/l）, completely, separation of solid and liquid obtains smart selenium to selenium precipitation；
D, the sodium sulfite solution Oxidation Leaching essence selenium with mass fraction 40% ~ 50%, it is 2 ~ 4 to control the solid mass ratio of liquid:1, leach
75 ~ 100 DEG C of temperature, extraction time is 2 ~ 4h, is then filtrated to get selenium-rich liquid；
E, toward the hot dilute sulfuric acid that 5 ~ 200g/l is slowly added in selenium-rich liquid, acidifying reduction, water-bath is incubated 2 ~ 3h, filtering, washing, dry
It is dry, high purity selenium is obtained.
In step a, selenium water quality ratio is 1 ~ 2 in slurry type feeding:2；
In step c, the method for Se content is in detection supernatant：The supernatant after the heavy selenium of 5ml is taken, the KI of 1ml is instilled
（10g/l）Blueness is occurred without, i.e. selenium precipitation is complete；
In step d, extraction temperature is 75 ~ 100 DEG C；
In step e, selenium precipitation is washed with the ethanol solution that volume fraction is 50%.
Embodiment 1
（1）Claim the high miscellaneous impure selenium 200g after drying first, with 200ml water slurrys, open stirring, be slowly added to 500ml mass point
Number is in 35% sodium hydroxide solution, extraction time is 1.5h, it is ensured that impure selenium is completely dissolved leaching；
（2）Alkali immersion liquid pH to 6.8 is adjusted with the hydrochloric acid of mass fraction 5%, the vulcanized sodium of 100g is added, stirred and evenly mixed, stand 1h
Filtering and impurity removing obtains alkali immersion liquid；
（3）Alkali immersion liquid continues to adjust pH to 1.2 with the hydrochloric acid of mass fraction 10%, is aged 2.5h, takes selenium in supernatant detection solution
Content（≤0.15g/l）, completely, separation of solid and liquid obtains smart selenium to selenium precipitation；
（4）With the sodium sulfite solution Oxidation Leaching of mass fraction 40% essence selenium, 75 ± 2 DEG C of temperature is controlled, extraction time is 2.5h,
Then it is filtrated to get selenium-rich liquid；
（5）The hot dilute sulfuric acid of 10g/l is slowly added to toward selenium-rich liquid, acidifying reduction is filtered after water-bath insulation 2.5h, uses volume integral
Number is 50% ethanol solution washing filter residue, dries prepared high purity selenium of the grade not less than 99.99%.
Embodiment 2
（1）Aqueous first 15% high miscellaneous impure selenium 260g, with 300ml water slurrys, opens stirring, is slowly added to 500ml mass fractions
For in 40% sodium hydroxide solution, extraction time is 2h, it is ensured that impure selenium is completely dissolved leaching；
（2）Alkali immersion liquid pH to 7.0 is adjusted with the hydrochloric acid of mass fraction 10%, the vulcanized sodium of 110g is added, stirred and evenly mixed, stood
1h filtering and impurity removings obtain alkali immersion liquid；
（3）The alkali immersion liquid hydrochloric acid of mass fraction 15% continues to adjust pH to 1.0, after stirring, is aged 3.0h, takes supernatant
Se content in detection solution（≤0.15g/l）, completely, separation of solid and liquid obtains smart selenium to selenium precipitation；
（4）With the sodium sulfite solution Oxidation Leaching of mass fraction 45% essence selenium, 85 ± 2 DEG C of temperature is controlled, extraction time is 3.0h,
Then it is filtrated to get selenium-rich liquid；
（5）The hot dilute sulfuric acid of 50g/l is slowly added to toward selenium-rich liquid, acidifying reduction is filtered after water-bath insulation 3.0h, uses volume integral
Number is 50% ethanol solution washing filter residue, dries prepared high purity selenium of the grade not less than 99.99.
Embodiment 3
（1）Aqueous first 20% high miscellaneous impure selenium 300g, pulpous state is tuned into 400ml water, is 45% hydroxide 500ml mass fractions
Sodium solution is repeatedly added in pulpous state impure selenium on a small quantity, stirring while adding, and the reaction time is 2.5h, it is ensured that impure selenium is completely dissolved leaching
Go out；
（2）Alkali immersion liquid pH to 7.0 is adjusted with the hydrochloric acid of mass fraction 15%, the vulcanized sodium of 120g is added, stirred and evenly mixed, stood
1h filtering and impurity removings obtain alkali immersion liquid；
（3）The alkali immersion liquid hydrochloric acid of mass fraction 20% continues to adjust pH to 1.0, after stirring, is aged 3.0h, takes supernatant
Se content in detection solution（≤0.15g/l）, completely, separation of solid and liquid obtains smart selenium to selenium precipitation；
（4）With the sodium sulfite solution Oxidation Leaching of mass fraction 50% essence selenium, 90 ± 2 DEG C of temperature is controlled, extraction time is 3.0h,
Then it is filtrated to get selenium-rich liquid；
（5）The hot dilute sulfuric acid of 50g/l is slowly added to toward selenium-rich liquid, acidifying reduction is filtered after water-bath insulation 3.0h, uses volume integral
Number is 50% ethanol solution washing filter residue, dries prepared high purity selenium of the grade not less than 99.99.
The present invention realizes two steps and leaches wet purification impure selenium preparation high purity selenium, shortens selenium purifying flow, improves
The rate of recovery, reduces production cost, reduces the limitation of large-scale production.
Above case study on implementation is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, in the ken that the field those of ordinary skill possesses, that is made within the spirit and principles in the present invention is any
Modification, equivalent substitute and improvement etc., are regarded as the protection domain of the application.
Claims (5)
1. a kind of method that use impure selenium wet purification prepares high purity selenium, it is characterised in that comprise the following steps：
A, impure selenium is first used into water slurry, use the mode of slurry type feeding to be slowly at the uniform velocity added to the hydrogen that mass fraction is for 35% ~ 50%
In sodium hydroxide solution, it is 3 ~ 5 to control the solid mass ratio of liquid:1, extraction time is 1.5 ~ 2h, it is ensured that impure selenium is completely dissolved leaching；
B, the hydrochloric acid regulation alkali immersion liquid pH to 6.5 ~ 7.0 with mass fraction 5 ~ 20%, add the vulcanization of 0.5 ~ 2 times of impure selenium dry weight
Sodium, stirs and evenly mixs, and stands 1h filtering and impurity removings；
C, alkali immersion liquid continue to adjust pH to 1.0 ~ 1.5 with the hydrochloric acid of mass fraction 10% ~ 30%, are aged 2.5 ~ 3h, take supernatant inspection
Survey Se content in solution（≤0.15g/l）, completely, separation of solid and liquid obtains smart selenium to selenium precipitation；
D, the sodium sulfite solution Oxidation Leaching essence selenium with mass fraction 40% ~ 50%, it is 2 ~ 4 to control the solid mass ratio of liquid:1, leach
75 ~ 100 DEG C of temperature, extraction time is 2 ~ 4h, is then filtrated to get selenium-rich liquid；
E, toward the hot dilute sulfuric acid that 5 ~ 200g/l is slowly added in selenium-rich liquid, acidifying reduction, water-bath is incubated 2 ~ 3h, filtering, washing, dry
It is dry, high purity selenium is obtained.
2. the method that a kind of use impure selenium wet purification according to claim 1 prepares high purity selenium, itself it is characterized in that：
In step a, selenium water quality ratio is 1 ~ 2 in slurry type feeding:2.
3. the method that a kind of use impure selenium wet purification according to claim 1 prepares high purity selenium, itself it is characterized in that：
In step c, the method for Se content is in detection supernatant：The supernatant after the heavy selenium of 5ml is taken, the KI of 1ml is instilled（10g/l）
Blueness is occurred without, i.e. selenium precipitation is complete.
4. the method that a kind of use impure selenium wet purification according to claim 1 prepares high purity selenium, itself it is characterized in that：
In step d, extraction temperature is 75 ~ 100 DEG C.
5. the method that a kind of use impure selenium wet purification according to claim 1 prepares high purity selenium, itself it is characterized in that：
In step e, selenium precipitation is washed with the ethanol solution that volume fraction is 50%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231175A (en) * | 2018-11-14 | 2019-01-18 | 昆明理工大学 | A method of impure selenium is purified with dehydrated alcohol |
| CN110745789A (en) * | 2019-11-01 | 2020-02-04 | 昆明理工大学 | Crude selenium purification method |
| CN110817811A (en) * | 2019-12-12 | 2020-02-21 | 昆明冶金研究院有限公司 | Preparation method of high-purity selenium powder with uniform particle size distribution |
| CN111689479A (en) * | 2020-07-01 | 2020-09-22 | 昆明冶金研究院有限公司 | Medicament SC-500 for removing As, Pb and Sb and preparation method and application thereof |
| CN115321492A (en) * | 2022-08-31 | 2022-11-11 | 云南铜业股份有限公司西南铜业分公司 | Method for extracting and purifying selenium under normal pressure |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231175A (en) * | 2018-11-14 | 2019-01-18 | 昆明理工大学 | A method of impure selenium is purified with dehydrated alcohol |
| CN110745789A (en) * | 2019-11-01 | 2020-02-04 | 昆明理工大学 | Crude selenium purification method |
| CN110817811A (en) * | 2019-12-12 | 2020-02-21 | 昆明冶金研究院有限公司 | Preparation method of high-purity selenium powder with uniform particle size distribution |
| CN111689479A (en) * | 2020-07-01 | 2020-09-22 | 昆明冶金研究院有限公司 | Medicament SC-500 for removing As, Pb and Sb and preparation method and application thereof |
| CN115321492A (en) * | 2022-08-31 | 2022-11-11 | 云南铜业股份有限公司西南铜业分公司 | Method for extracting and purifying selenium under normal pressure |
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Inventor after: Wu Bing Inventor after: Zhang Huijuan Inventor after: Wu Xinping Inventor after: Xu Juan Inventor after: Nan Lizhi Inventor after: Sun Jiafa Inventor after: Meng Weifen Inventor after: Li Guangyou Inventor after: Wang Zhilin Inventor after: Liu Yafang Inventor before: Wu Xinping Inventor before: Zhang Huijuan Inventor before: Wu Bing Inventor before: Xu Juan Inventor before: Nan Lizhi Inventor before: Li Guangyou Inventor before: Wang Zhilin Inventor before: Zhang Guohui Inventor before: Hu Chao Inventor before: Zhan Hongbo |
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