CN102583268A - Method for extracting selenium from low-grade complex material - Google Patents
Method for extracting selenium from low-grade complex material Download PDFInfo
- Publication number
- CN102583268A CN102583268A CN2012100458557A CN201210045855A CN102583268A CN 102583268 A CN102583268 A CN 102583268A CN 2012100458557 A CN2012100458557 A CN 2012100458557A CN 201210045855 A CN201210045855 A CN 201210045855A CN 102583268 A CN102583268 A CN 102583268A
- Authority
- CN
- China
- Prior art keywords
- selenium
- low
- washing
- selenium powder
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a method for extracting selenium from a low-grade complex material. The method is characterized by comprising the following steps of: adding a selenium material into a sodium hydroxide solution for reaction and then filtering; carrying out sulfating roasting on filter residue; reducing smoke with SO2 to separate out sediment; filtering, washing and drying to obtain washed selenium powder; regulating the pH value of a filtrate with diluted sulfuric acid, filtering, washing and drying to obtain selenium powder; and regulating the acidity of the solution obtained after decomposition, and reducing to obtain reduced selenium powder. According to the invention, the purity of the selenium powder produced by using the method reaches above 95%, and the recovery rate of selenium reaches more than 98%. The method disclosed by the invention is a high-recovery-rate short-flow, little-pollution low-cost method for extracting selenium from the low-grade selenium material.
Description
Technical field
The present invention relates to a kind of process for extracting of selenium, particularly relate to a kind of method of from the low-grade complex material, extracting selenium.Belong to the dissipated metal metallurgical technology field.
Background technology
Selenium is a kind of dissipated metal element, and content is extremely low in the earth's crust, and Clark value is lower than 5 * 10
-5%, very difficult formation independently has the mineral deposit that commercial mining is worth, and selenium all is comprehensive recovery from the sub product of nonferrous metallurgical process, thereby the output of selenium is very low.According to U.S. Minerals Yearbook statistics, Chinese annual selenium consumption 1097t in 2008, and domestic selenium is from output 316 t only, the overwhelming majority relies on external import.The range of application of selenium is very extensive, mainly is as the electrolytic manganese industry, accounts for the 30-50% of total amount, secondly be industries such as xerox, glass, chemical industry, metallurgy, electronics, and selenium has unique purposes in military project, medical treatment and traffic department.In recent years, along with the continuous expansion of range of application, worldwide supply falls short of demand for selenium, causes its price constantly to rise violently.Therefore, the technological method of research and development extraction selenium has application market background widely.
Along with domestic and international selenium consumption market continues vigorous; Selenium output and production capacity all are the growth situation; Cause tractable selenium resource scarcity; Especially grade more than 80%, tractable selenium raw material supply shortage, but also find to exist on the market low-grade in a large number, complicated component selenium material (containing selenium 20-60%) simultaneously.If this type material is directly as raw material production tin anhydride or selenium powder, because raw material impurity content is high and part selenium exists with the intermetallic compound form, selenium is difficult to effectively separate with impurity, causes that production efficiency is low, cost is high, is difficult to guarantee quality product simultaneously.
The selenium grade is low, impurity is high, be allowed for access after the further removal of impurities of need, the refining selenium powder, tin anhydride product line.At present method of refining mainly contains with strong oxidizers such as nitric acid or VAL-DROP the oxidation of selenium material, makes selenolite change into selenous acid, behind the purification and impurity removal, restores and obtains thick selenium powder.In dissolution process, use nitric acid or VAL-DROP, the nitrogen peroxide of generation or chlorine damage by fume are bigger, and equipment corrosion is serious, selenium recovery only 80～85%.Another kind of refinery practice is with the material sulfurization roasting, because the mud acid ratio is too little, it is very incomplete that bakes to burn the article steams selenium, need carry out repeatedly roasting and steam selenium, causes fuel consumption big, and working cycle is long, and production efficiency is low.
Summary of the invention
The object of the invention aims to provide the method from low-grade selenium material extraction selenium that a kind of recovery is high, flow process is short, pollution is little, cost is low.
Method of the present invention is realized by following measure:
It is the sodium hydroxide solution of 100～300g/L that the selenium material is added concentration, solid-to-liquid ratio 1:3～6,60～100 ℃ of temperature of reaction; 4～6 hours reaction times, filter, filter residue is allocated 80～120% heavy sulfuric acid of slag into; In 450～550 ℃ of roasting temperatures 3～6 hours, flue gas in the absorption tower by SO
2Settling is separated out in reduction, after filtration, washing, drying, obtains 95～98% washing selenium powders.
Using dilute sulphuric acid to regulate filtrating pH is 6～10, and 60～100 ℃ of temperature of reaction in 2～4 hours reaction times, through filtration, washing, oven dry, obtain selenium powder and contain selenium 95～99%.After decomposition, add sulfuric acid regulation solution acidity 50～150g/L in the liquid, adopt SO
2, the reduction of thiocarbamide, S-WAT, 60～100 ℃ of temperature of reaction, 3～5 hours reaction times, through filter, washing, dry after, the selenium powder that obtains reducing contains selenium 95～99%.This method selenium recovery reaches more than 98%.
Fig. 1 is the schema of the inventive method.
Embodiment
Embodiment 1
To contain the material of selenium 32.7%, lead 5.2%, copper 4.5%, silicon 7.8%, adding concentration is the sodium hydroxide solution of 200g/L, solid-to-liquid ratio 1:4; 90 ℃ of reaction times; In 4 hours reaction times, filter residue contains selenium 6.5%, is equipped with 105% heavy sulfuric acid of slag; 450 ℃ of roasting temperatures 4 hours, the washing selenium powder contains selenium 97%.
Using dilute sulphuric acid to regulate filtrating pH is 8, and 90 ℃ of temperature of reaction in 2 hours reaction times, through filtration, washing, oven dry, obtain selenium powder and contain selenium 97.5%.Decompose back liquid and add sulfuric acid adjusting acidity, adopt SO to 100g/L
2, the reduction of thiocarbamide, S-WAT, 90 ℃ of temperature of reaction, 3 hours reaction times, through filter, washing, oven dry, the selenium powder that obtains reducing contains selenium 98.4%, reduction back liquid contains selenium 45mg/L.Selenium recovery is 98.6%.
Embodiment 2
To contain the material of selenium 32.7%, lead 5.2%, copper 4.5%, silicon 7.8%, adding concentration is the sodium hydroxide solution of 250g/L, solid-to-liquid ratio 1:5; 90 ℃ of reaction times; In 4 hours reaction times, filter residue contains selenium 5.9%, is equipped with 100% heavy sulfuric acid of slag; 450 ℃ of roasting temperatures 4 hours, the washing selenium powder contains selenium 97.2%.
Using dilute sulphuric acid to regulate filtrating pH is 8, and 90 ℃ of temperature of reaction in 2 hours reaction times, through filtration, washing, oven dry, obtain selenium powder and contain selenium 97.5%.Decompose back liquid and add sulfuric acid adjusting acidity, adopt SO to 150g/L
2, the reduction of thiocarbamide, S-WAT, 90 ℃ of temperature of reaction, 3 hours reaction times, through filter, washing, oven dry, the selenium powder that obtains reducing contains selenium 98.5%, reduction back liquid contains selenium 40mg/L.Selenium recovery is 99.0%.
Claims (3)
1. a method of from the low-grade complex material, extracting selenium is characterized in that it is the sodium hydroxide solution of 100～300g/L that the selenium material is added concentration, solid-to-liquid ratio 1:3～6; 60～100 ℃ of temperature of reaction; 4～6 hours reaction times, filter, filter residue is allocated 80～120% heavy sulfuric acid of slag into; In 450～550 ℃ of roasting temperatures 3～6 hours, flue gas in the absorption tower by SO
2Settling is separated out in reduction, after filtration, washing, drying, obtains washing selenium powder.
2. using dilute sulphuric acid to regulate filtrating pH is 6～10, and 60～100 ℃ of temperature of reaction in 2～4 hours reaction times, through filtration, washing, oven dry, obtain selenium powder.
3. after decomposition, add sulfuric acid regulation solution acidity 50～150g/L in the liquid, adopt SO
2, the reduction of thiocarbamide, S-WAT, 60～100 ℃ of temperature of reaction in 3～5 hours reaction times, obtain reducing selenium powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100458557A CN102583268A (en) | 2012-02-28 | 2012-02-28 | Method for extracting selenium from low-grade complex material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100458557A CN102583268A (en) | 2012-02-28 | 2012-02-28 | Method for extracting selenium from low-grade complex material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102583268A true CN102583268A (en) | 2012-07-18 |
Family
ID=46472634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100458557A Pending CN102583268A (en) | 2012-02-28 | 2012-02-28 | Method for extracting selenium from low-grade complex material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102583268A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523757A (en) * | 2013-10-31 | 2014-01-22 | 佛山市南海万兴材料科技有限公司 | A processing process for extracting selenium from waste acid water containing cadmium selenium |
| CN105063361A (en) * | 2015-08-20 | 2015-11-18 | 江西铜业股份有限公司 | Method for comprehensively recovering valuable metal from copper anode slime |
| CN105219958A (en) * | 2015-11-16 | 2016-01-06 | 湖南城市学院 | A kind of alkali oxide leaching is separated the method for selen-tellurjum enriching noble metals |
| CN106379870A (en) * | 2016-08-25 | 2017-02-08 | 浙江亚栋实业有限公司 | Method for recovery of selenium from copper anode mud |
| CN108559850A (en) * | 2018-06-11 | 2018-09-21 | 中南大学 | A method of recycling selen-tellurjum from the mud of waste acid containing selenium |
| CN112795782A (en) * | 2020-12-26 | 2021-05-14 | 黑龙江紫金铜业有限公司 | Method for separating selenium, mercury and lead from acid mud through chlorination leaching |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2618395A1 (en) * | 1976-04-27 | 1977-11-10 | Preussag Ag Metall | Pure tellurium dioxide prodn. from granular tellurium - by oxidn. with conc. sulphuric acid, dissolution in alkali and pptn. |
| CN101434385A (en) * | 2008-12-08 | 2009-05-20 | 阳谷祥光铜业有限公司 | Process for extracting tellurium from copper anode mud |
-
2012
- 2012-02-28 CN CN2012100458557A patent/CN102583268A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2618395A1 (en) * | 1976-04-27 | 1977-11-10 | Preussag Ag Metall | Pure tellurium dioxide prodn. from granular tellurium - by oxidn. with conc. sulphuric acid, dissolution in alkali and pptn. |
| CN101434385A (en) * | 2008-12-08 | 2009-05-20 | 阳谷祥光铜业有限公司 | Process for extracting tellurium from copper anode mud |
Non-Patent Citations (2)
| Title |
|---|
| O.HYVARINEN等: "奥托昆普波里精炼厂从铜阳极泥中回收硒及贵金属", 《中国有色冶金》, 1987, pages 39 - 44 * |
| 蔡世兵: "从高品位硒、碲废料中分离回收硒和碲", 《湿法冶金》, vol. 27, no. 1, March 2008 (2008-03-01) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523757A (en) * | 2013-10-31 | 2014-01-22 | 佛山市南海万兴材料科技有限公司 | A processing process for extracting selenium from waste acid water containing cadmium selenium |
| CN103523757B (en) * | 2013-10-31 | 2015-06-03 | 佛山市南海万兴材料科技有限公司 | A processing process for extracting selenium from waste acid water containing cadmium selenium |
| CN105063361A (en) * | 2015-08-20 | 2015-11-18 | 江西铜业股份有限公司 | Method for comprehensively recovering valuable metal from copper anode slime |
| CN105063361B (en) * | 2015-08-20 | 2017-03-22 | 江西铜业股份有限公司 | Method for comprehensively recovering valuable metal from copper anode slime |
| CN105219958A (en) * | 2015-11-16 | 2016-01-06 | 湖南城市学院 | A kind of alkali oxide leaching is separated the method for selen-tellurjum enriching noble metals |
| CN106379870A (en) * | 2016-08-25 | 2017-02-08 | 浙江亚栋实业有限公司 | Method for recovery of selenium from copper anode mud |
| CN108559850A (en) * | 2018-06-11 | 2018-09-21 | 中南大学 | A method of recycling selen-tellurjum from the mud of waste acid containing selenium |
| CN108559850B (en) * | 2018-06-11 | 2019-10-22 | 中南大学 | A method of recycling selen-tellurjum from the mud of waste acid containing selenium |
| CN112795782A (en) * | 2020-12-26 | 2021-05-14 | 黑龙江紫金铜业有限公司 | Method for separating selenium, mercury and lead from acid mud through chlorination leaching |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102534228B (en) | Method for comprehensively recovering valuable elements from high-arsenic-containing copper smelting soot | |
| CN100591783C (en) | Method for recovering zinc and lead from waste electrolytic anode mud | |
| CN102583268A (en) | Method for extracting selenium from low-grade complex material | |
| CN101451199B (en) | Method for extracting vanadic anhydride from stone coal vanadium ore | |
| CN101503761B (en) | Method for separating and recycling valuable metal from pressure leached high sulphur slag | |
| CN104178642B (en) | A kind of method of zinc and iron in separation of Zinc leached mud | |
| CN103449517B (en) | Method for preparing white arsenic from arsenic-containing dust in evaporation-free manner | |
| CN102094128B (en) | Method for comprehensively recovering various valuable metals from germanium-containing material by wet process | |
| CN102286759B (en) | Method for preparing electrodeposited zinc from high-fluorine high-chlorine secondary zinc oxide powder | |
| CN102390819B (en) | Method for preparing tellurium dioxide from tellurium slag | |
| CN101538646A (en) | Process method for producing copper sulfate by intensified leaching of copper-containing materials | |
| CN103924091A (en) | Smelting method for removing fluorine and chlorine out of fluorine-and-chlorine-containing inferior zinc oxide and enriching valuable metals | |
| CN102923764B (en) | Method for preparing sodium stannate from stannic oxide and sodium salt in reduction roasting manner | |
| CN101450814A (en) | Novel method for extracting vanadic anhydride from stone coal vanadium ore | |
| CN102312102A (en) | Comprehensive utilization method for titanium-contained blast furnace slag | |
| CN102690947A (en) | Smelting process of silver concentrate | |
| CN102230080B (en) | Method for zinc raw material dechlorination in zinc hydrometallurgy | |
| CN1298619C (en) | Method for removing tellurium from coarse selenium | |
| CN102643986A (en) | Method for producing electrolytic manganese by taking pyrolusite as raw material through wet method reduction leaching | |
| CN104232889A (en) | Technology for producing electrolytic metal manganese from low-grade manganese mine | |
| CN101768668B (en) | Method for comprehensive recovery of lead and tin from alkaline refining slag of lead | |
| CN101525696A (en) | Method for leaching indium from leaching residue containing indium | |
| CN103395751A (en) | Wet method used for extracting products from low-grade complex material containing tellurium and selenium | |
| CN103233129B (en) | Wet-process open treatment method of arsenic in copper ashes | |
| CN104609472A (en) | Method for producing vanadium pentoxide from titanium tetrachloride refinement vanadium-removal slurry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120718 |