CN109231175A - A method of impure selenium is purified with dehydrated alcohol - Google Patents

A method of impure selenium is purified with dehydrated alcohol Download PDF

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Publication number
CN109231175A
CN109231175A CN201811352997.1A CN201811352997A CN109231175A CN 109231175 A CN109231175 A CN 109231175A CN 201811352997 A CN201811352997 A CN 201811352997A CN 109231175 A CN109231175 A CN 109231175A
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CN
China
Prior art keywords
selenium
dehydrated alcohol
impure
sodium thiosulfate
precipitating
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Pending
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CN201811352997.1A
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Chinese (zh)
Inventor
蒋文龙
杨斌
查国正
刘大春
徐宝强
陈秀敏
李夫
李一夫
郁青春
杨红卫
田阳
邓勇
王飞
熊恒
杨佳
曲涛
孔令鑫
郭新宇
邓聚海
黄大鑫
周毅
程明强
高哲
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201811352997.1A priority Critical patent/CN109231175A/en
Publication of CN109231175A publication Critical patent/CN109231175A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00Selenium; Tellurium; Compounds thereof
    • C01B19/02Elemental selenium or tellurium

Abstract

The present invention discloses a kind of method with dehydrated alcohol purification impure selenium, belongs to hydrometallurgy field of engineering technology.The method of the invention is leached impure selenium (containing selenium 90% ~ 99%) using sodium sulfite solution, and extraction temperature is 50~150 DEG C, and extraction time is 0.5~3h, and mixing speed is 100~350r/min.Sodium thiosulfate leachate is obtained by filtration after leaching, obtained sodium thiosulfate leachate and excessive dehydrated alcohol are mixed to obtain selenium precipitating, last selenium precipitating obtains the smart selenium that purity is 99.99% ~ 99.999% after washing, filtering, drying.The metal impurities such as tellurium, lead, copper, silver, gold in leached mud are further enriched with.Selenium is precipitated from sodium thiosulfate solution using dehydrated alcohol in the present invention, to realize the high efficiency extraction and purification of selenium, whole process does not have exhaust gas, waste residue to generate.

Description

A method of impure selenium is purified with dehydrated alcohol
Technical field
The present invention relates to a kind of methods with dehydrated alcohol purification impure selenium, belong to hydrometallurgy field of engineering technology.
Technical background
Selenium is dissipated metal, and the critical role in national economy and human health is more and more prominent.Selenium has widely Application field is mainly used for electronics industry such as photoelectric tube, solar battery, pigment industry.In terms of human health, selenium is human body One of required microelement, selenium-enriched food also receives extensive concern, also functions to key effect in the synthesis of human cytotoxic drug. The production of high-purity selenium is also paid much attention to;For a long time, the selenium of China's production is mainly that the technical grade of 98% or more purity produces Product seriously limit the exploitation of high-tech new material, and the selenium of higher purity is dependent on external a large amount of imports.
There is 90% selenium mainly to recycle and obtain from the copper electrolyzing refining earth of positive pole earth of positive pole in the world at present, but is often associated with There are many impurity such as Te, Pb, Cu, Ag, S, needs further to purify.At present according to purification principle, the method for purification of selenium is mainly divided For physical purification and chemical purification two major classes.Physical method has vacuum distillation method, zone melting method etc..Vacuum distillation method can efficiently divide From the high-melting-points such as copper, silver, gold, low saturated vapour pressure impurity, but reduced levels are difficult to remove for impurity such as Te, Pb, S;Area Domain smelting process is a kind of effective ways purified metals, but the production cycle is longer, is not suitable for large-scale production.Chemical method has impure selenium Voloxidation-sulfur dioxide reduction method, hydrogen selenide thermal decomposition method, Arbiso process and solvent extraction and ion-exchange etc.; Oxygen volatilization-sulfur dioxide reduction method experimental condition is more demanding, and process flow is complicated, and working condition is poor, pollutes environment;Selenizing Hypertoxic gas hydrogen selenide can be generated during hydrogen thermal decomposition method purification selenium, institute in this way only can a small amount of high purity selenium.Sulfurous Sour sodium method can effectively remove the impurity that vacuum distillation method is difficult to remove, and this method is the sodium sulfite solution that heat is dissolved in using selenium In and impurity is insoluble, selenium infusion solution by filtering, be precipitated selenium after crystallisation by cooling naturally, but natural precipitation process exist it is time-consuming Long, the disadvantages of rate of recovery is extremely low.Compared with the method for purification of selenium is precipitated naturally in traditional handicraft sodium sulfite solution leaching-, this hair The bright precipitation for promoting selenium using dehydrated alcohol, can be obviously shortened the precipitation time of selenium, greatly improve smart selenium recovery.
Summary of the invention
The present invention provides a kind of methods with dehydrated alcohol purification impure selenium, can obtain the higher smart selenium of purity, and mistake Journey is simple, not can cause environmental pollution without waste water generation, and cost is lower, specifically includes the following steps:
(1) impure selenium raw material is dissolved in sodium sulfite solution, sodium thiosulfate leachate is obtained by filtration after agitating and heating;
(2) at normal temperature, obtained sodium thiosulfate leachate and dehydrated alcohol are mixed to be precipitated and obtain selenium precipitating;
(3) selenium precipitating is filtered, washed, is dried to obtain the smart selenium that purity is 99.99% ~ 99.999%.
Preferably, the selenium powder that impure selenium material purity of the present invention is 90% ~ 99%, selenium powder cross 50 meshes.
Preferably, the concentration of sodium sulfite solution of the present invention is that 300g/L, sodium sulfite solution and impure selenium are solid by liquid Than for (5 ~ 20): 1 ratio is added in reaction kettle simultaneously;Heating temperature is 50~150 DEG C, 0.5~3h of heating time, stirring speed Degree is 100~350r/min.
Preferably, the volume of dehydrated alcohol of the present invention is greater than the volume of sodium thiosulfate leachate.
Preferably, filtering of the present invention needs twice, and drying temperature is 60 DEG C.
Leachate first is obtained to impure selenium feedstock purification using Arbiso process in the present invention, sodium sulfite solution dissolution is thick Selenium is wet process reaction, and the main chemical reactions of generation are as follows:
Se(s) + Na2SO3(aq) = Na2SeSO3(aq)
Beneficial effects of the present invention:
The present invention not only promotes selenium using dehydrated alcohol and is precipitated from sodium thiosulfate solution, but also realizes the high efficiency extraction of selenium With purification, whole process does not have exhaust gas, waste residue to generate, and waste liquid, which can evaporate to isolate dehydrated alcohol and continue Returning process, to be used for from selenium Selenium is extracted in sodium thiosulfate solution, finally obtains to obtain the smart selenium that purity is 99.99% ~ 99.999%.
Detailed description of the invention
Fig. 1 is flow diagram of the invention.
Specific embodiment
Below in conjunction with the embodiment in the present invention, clear, complete description is carried out to technical solution of the present invention, but send out Bright protection scope is not limited to the content.
Embodiment 1
A method of impure selenium being purified with dehydrated alcohol, specifically includes the following steps:
Impure selenium raw material is crushed, crosses 50 meshes, the sodium sulfite solution 300ml and purity for then preparing 300g/L are 90% Impure selenium raw material by liquid-solid ratio be 15:1 simultaneously be added in reaction kettle, controlled at 120 DEG C, mixing speed 350r/min, 3h is reacted under oil bath heating, magnetic agitation, leachate containing selenium is obtained by filtration.
It measures excessive dehydrated alcohol with graduated cylinder to be added in sodium thiosulfate leachate, low whipping speed 320r/min Under conditions of be instantly available selenium precipitating, selenium precipitating is using obtaining smart selenium after being filtered, washed, drying (60 DEG C);The Chinese referring in The people republic non-ferrous metal industry standard YS/T223-2007 and YS/T226.13-2009, using inductively coupled plasma constitution Spectrometer (ICP-MS) detects the purity of smart selenium.The purity of smart selenium is 99.991%, and the leaching rate of selenium is 97.53%, comprehensive Direct yield is 94.3562%.
Table 1: 1 impure selenium of embodiment (Se 90%) purifies result
Embodiment 2
A method of impure selenium being purified with dehydrated alcohol, specifically includes the following steps:
Impure selenium raw material is crushed, crosses 50 meshes, the sodium sulfite solution 300ml and purity for preparing 300g/L are 93% impure selenium Raw material is that 20:1 is added in reacting furnace simultaneously by liquid-solid ratio, and controlled at 110 DEG C, mixing speed 300r/min, machinery is stirred Lower reaction 2h is mixed, sodium thiosulfate leachate is obtained by filtration.
It is added in sodium thiosulfate leachate with the excessive dehydrated alcohol of graduated cylinder measurement and obtains selenium precipitating, selenium precipitating passes through again Be filtered, washed, dry (60 DEG C) after obtain smart selenium;Obtained smart selenium is referring to People's Republic of China's non-ferrous metal industry standard YS/T223-2007 and YS/T226.13-2009, using icp ms (ICP-MS) to the purity of smart selenium It is detected.The purity of smart selenium is 99.993%, and the leaching rate of selenium is 97.63%, and comprehensive direct yield is 94.65%.
Table 2: 2 impure selenium of embodiment (Se 93%) purifies result
Embodiment 3
A method of impure selenium being purified with dehydrated alcohol, specifically includes the following steps:
Impure selenium raw material is crushed, crosses 50 meshes, impure selenium raw material is handled, the sodium sulfite solution of 300g/L is prepared It by liquid-solid ratio is that 9:1 is added in reacting furnace simultaneously that 300ml and purity, which are 99% impure selenium raw material, controlled at 50 DEG C, mixing speed For 200r/min, 1.5h is reacted under mechanical stirring, sodium thiosulfate leachate is obtained by filtration.
It is added in sodium thiosulfate leachate with the excessive dehydrated alcohol of graduated cylinder measurement and obtains selenium precipitating, selenium precipitating passes through again Be filtered, washed, dry (60 DEG C) after obtain smart selenium;Obtained smart selenium is referring to People's Republic of China's non-ferrous metal industry standard YS/T223-2007 and YS/T226.13-2009, using icp ms (ICP-MS) to the purity of smart selenium It is detected.The purity of smart selenium is 99.9990%, and the leaching rate of selenium is 97.6324%, and comprehensive direct yield is 94.6522%.
Table 3: 3 impure selenium of embodiment (Se 99%) purifies result

Claims (5)

1. a kind of method with dehydrated alcohol purification impure selenium, which is characterized in that specifically includes the following steps:
(1) impure selenium raw material is dissolved in sodium sulfite solution, sodium thiosulfate leachate is obtained by filtration after agitating and heating;
(2) at normal temperature, obtained sodium thiosulfate leachate and dehydrated alcohol are mixed to be precipitated and obtain selenium precipitating;
(3) selenium precipitating is filtered, washed, is dried to obtain smart selenium.
2. method according to claim 1, it is characterised in that: the selenium powder that impure selenium material purity is 90% ~ 99%, selenium powder cross 50 mesh Sieve.
3. method according to claim 1, it is characterised in that: the concentration of sodium sulfite solution is 300g/L, and sodium sulfite is molten Liquid and impure selenium are (5 ~ 20) in liquid-solid ratio: 1 ratio is added in reaction kettle simultaneously;Heating temperature is 50~150 DEG C, heating time 0.5~3h, mixing speed are 100~350r/min.
4. method according to claim 1, it is characterised in that: the volume of dehydrated alcohol is greater than the body of sodium thiosulfate leachate Product.
5. method according to claim 1, which is characterized in that filtering needs twice, and drying temperature is 60 DEG C.
CN201811352997.1A 2018-11-14 2018-11-14 A method of impure selenium is purified with dehydrated alcohol Pending CN109231175A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109911869A (en) * 2019-03-12 2019-06-21 湖南工业大学 A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition
CN110668471A (en) * 2019-10-22 2020-01-10 成都市科隆化学品有限公司 Purification production method of environment-friendly potassium persulfate
CN111517290A (en) * 2020-05-12 2020-08-11 昆明冶金研究院有限公司 Method for preparing refined selenium by two-step method
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
CN112125284A (en) * 2020-08-31 2020-12-25 河南师范大学 Preparation method and medical application of amorphous nano-selenium with biological activity

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57179004A (en) * 1981-04-28 1982-11-04 Asahi Glass Co Ltd Refining method for metallic selenium
US4548800A (en) * 1982-08-02 1985-10-22 Xerox Corporation Process for selenium purification
CN102086029A (en) * 2010-12-04 2011-06-08 金川集团有限公司 Method for extracting selenium from selenium-contained material
CN103903868A (en) * 2014-03-17 2014-07-02 东南大学 Method for preparing CuSe back electrode of sensitization battery with activated Se disproportionation at room temperature
CN104743526A (en) * 2015-03-27 2015-07-01 大冶有色金属有限责任公司 Refining process of crude selenium
CN106853959A (en) * 2016-09-19 2017-06-16 三门峡市有色金属质量科学研究所 A kind of method that use impure selenium wet method prepares high purity selenium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57179004A (en) * 1981-04-28 1982-11-04 Asahi Glass Co Ltd Refining method for metallic selenium
US4548800A (en) * 1982-08-02 1985-10-22 Xerox Corporation Process for selenium purification
CN102086029A (en) * 2010-12-04 2011-06-08 金川集团有限公司 Method for extracting selenium from selenium-contained material
CN103903868A (en) * 2014-03-17 2014-07-02 东南大学 Method for preparing CuSe back electrode of sensitization battery with activated Se disproportionation at room temperature
CN104743526A (en) * 2015-03-27 2015-07-01 大冶有色金属有限责任公司 Refining process of crude selenium
CN106853959A (en) * 2016-09-19 2017-06-16 三门峡市有色金属质量科学研究所 A kind of method that use impure selenium wet method prepares high purity selenium

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109911869A (en) * 2019-03-12 2019-06-21 湖南工业大学 A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition
CN110668471A (en) * 2019-10-22 2020-01-10 成都市科隆化学品有限公司 Purification production method of environment-friendly potassium persulfate
CN111517290A (en) * 2020-05-12 2020-08-11 昆明冶金研究院有限公司 Method for preparing refined selenium by two-step method
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
CN112125284A (en) * 2020-08-31 2020-12-25 河南师范大学 Preparation method and medical application of amorphous nano-selenium with biological activity

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