CN103667695A - Method for extracting arsenic from gold ore - Google Patents
Method for extracting arsenic from gold ore Download PDFInfo
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- CN103667695A CN103667695A CN201310657811.4A CN201310657811A CN103667695A CN 103667695 A CN103667695 A CN 103667695A CN 201310657811 A CN201310657811 A CN 201310657811A CN 103667695 A CN103667695 A CN 103667695A
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Abstract
A method for extracting arsenic from gold ore is characterized by comprising the following steps: taking acidithiobacillus ferrooxidans as a leaching bacterial strain, taking ammonium sulfate, potassium chloride, dipotassium hydrogen phosphate, calcium nitrate and ferrous sulphate as a medium, so as to obtain a bacteria nutrient solution; adding arsenic-containing gold ore powder into the bacteria nutrient solution to prepare an ore pulp, and performing pre-oxidation on ore pulp bacteria; stopping pre-oxidation, filtering and washing the ore pulp; recovering arsenic from the solution, and using the pre-oxidation slag to extract gold; adjusting the pH value of the arsenic-containing solution with sodium hydroxide, filtering, adding copper sulfate into the filtrate, adjusting the pH value of the solution, and performing precipitation, filtering and washing to obtain copper arsenite; and adjusting the pH value of the filtrate from which copper arsenite is precipitated by using calcium oxide, removing precipitation, neutralizing with sulfuric acid and discharging the wastewater reaching the standard. The method provided by the invention is capable of effectively leaching out harmful element arsenic from ore, and the leaching rate of arsenic is more than 90%, so that the arsenic content in ore is substantially reduced, and the comprehensive recovery utilization of arsenic resource in ore is realized.
Description
Technical field
The present invention relates to a kind of method of extracting arsenic from Gold Ore.
Background technology
Gold is wrapped in containing the ore among the sulfide mineral of arsenic with form micro-or inferior micro-even Lattice Gold, belongs to extremely difficult ore.China's treating refractory As-containing gold ore stone resource is abundanter, and (in gold metal amount) according to incompletely statistics, approximately has 2000 tons of left and right.Adopt conventional cyanidation gold extraction technology to process, the leaching yield of gold is very low, is generally 20 ~ 50%.Main because this class ore is in cyanidation-leaching process, and gold is difficult to combine with leaching medicament, and because the sulfide solubleness of arsenic in solution is higher, prussiate and dissolved oxygens in can a large amount of consumption solution during cyaniding.After direct cyanide gold-leaching, the harmful elements such as arsenic in ore exist in solid waste in addition, easily cause secondary pollution.
Improve the cyanide leaching of this type of Results of Gold in Auriferous Ore Samples, must before Cyanide Leaching, carry out pre-oxidation treatment.Both at home and abroad treating refractory As-containing gold ore stone oxidation pre-treatment technology is mainly contained roasting oxidation method, presses hot extraction and stirs drill traverse bacterial oxidation method etc. at present.All there is certain defect in this several method, roasting oxidation method produces the toxic gases such as a large amount of sulfurous gas and white arsenic, serious environment pollution in roasting process; Press hot extraction to require equipment and materials high, investment is large, and operative technique requires strict, and method cost is high; Stir drill traverse bacterial oxidation method processing cost lower, but in production technique, adopt lime neutralization precipitation method to process arsenic-containing waste water, produce a large amount of arsenic throw outs that contain, have secondary pollution risk.
Summary of the invention
Object of the present invention is exactly the defect that will overcome prior art, and a kind of method of extracting arsenic from treating refractory As-containing gold ore stone is provided.The comprehensive harmful element arsenic reclaiming in ore, in destruction Gold Ore, the crystalline structure of arsenic mineral, makes to be wrapped gold and comes out, and improves golden Cyanide Leaching effect.
The concrete steps of the inventive method are as follows:
(1) spawn culture: the acidithiobacillus ferrooxidans (Acidithiobacillus ferrooxidans) of take is ore leaching strain, with ammonium sulfate 2 ~ 6g/L, Repone K 0.1 ~ 0.2g/L, dipotassium hydrogen phosphate 0.1 ~ 1g/L, nitrocalcite 0.01 ~ 0.03g/L, ferrous sulfate 20 ~ 50g/L is made into liquid nutrient medium, pH1.5 ~ 2.0, after inoculated bacteria, 24 ~ 48h is cultivated in inflation, obtains inoculum;
(2) arsenic mineral Bacterial Pre-oxidation: granularity is added in inoculum for-0.043mm accounts for 75 ~ 95% arsenic-containing gold ore stone flour, be made into solids concentration massfraction and be 10 ~ 30% ore pulp, in Bacterial Pre-oxidation condition, be: slurry pH 1.5 ~ 2.0,25 ~ 45 ℃ of temperature, aeration quantity 2 ~ 8L/L.min, stirring velocity be 400 ~ 600rpm to ore pulp Bacterial Pre-oxidation, oxidization time 3 ~ 10 days; Regularly detect arsonium ion content in solution, when arsonium ion content tends towards stability in solution, end preoxidation, filter, washing ore pulp; From solution, reclaim arsenic, preoxidation slag is used for extracting gold from;
(3) recovery of arsenic in solution: regulating the pH value of above-mentioned arsenic containing solution with solid sodium hydroxide is 5.5 ~ 6.5, after filtration, by copper and arsenic mol ratio, it is 2: 1, in filtrate, add copper sulfate, regulator solution pH value is 8.0 ~ 8.5, stirring reaction 1 ~ 2h, through precipitation, filtration, washing, obtains cupric arsenite; With calcium oxide, regulating the filtrate pH value after precipitation cupric arsenite is 8.5 ~ 9.5, removes precipitation, and with sulfuric acid, being neutralized to pH value is 6.5 ~ 7.5 rear qualified discharges.
The bacterial classification that the present invention uses is acidithiobacillus ferrooxidans (Acidithiobacillus ferrooxidans); Depositary institution: China Committee for Culture Collection of Microorganisms's common micro-organisms center; Preserving number: CGMCC No.1832(China Patent No. ZL 200610140866.8).
The cupric arsenite that the present invention obtains can adopt hydrometallurgical processes to be converted into white arsenic and copper sulfate.
Compare advantage of the present invention with existing conventional art:
1. method of the present invention can be destroyed the crystalline structure of arsenic mineral in treating refractory As-containing gold ore stone, and the micro-or inferior micro-even Lattice Gold being wrapped up by arsenic mineral is come out, and can improve the cyanide leaching of Gold in Ores.
2. method of the present invention can effectively leach the harmful element arsenic in ore, and the leaching yield of arsenic is greater than 90%, has significantly reduced the content of arsenic in ore.So both can reduce the consumption of sodium cyanide in cyaniding process, also reduce the Pollution risk of Cyanide Leaching slag to environment simultaneously.
3. method of the present invention can reclaim harmful element arsenic with the form of cupric arsenite from Bacterial Pre-oxidation solution, has realized the comprehensive reutilization of arsenic resource in ore.
4. method of the present invention produces without waste gas, and discharged wastewater met the national standard is conducive to environment protection; Microorganism, chemical reaction medicament that the present invention uses are substantially nontoxic, have guaranteed the security of producing.
Embodiment
By following instance, the invention will be further described.
Embodiment 1
In certain high arsenic golden ore concentrate hard to treat, containing arsenic 5.50%, gold grade is 40g/t ore, and granularity accounts for 90.50%, adopts steps of processing for-0.043mm:
(1) spawn culture: take acidithiobacillus ferrooxidans as ore leaching strain, with ammonium sulfate 5g/L, Repone K 0.1g/L, dipotassium hydrogen phosphate 0.5g/L, nitrocalcite 0.02g/L, ferrous sulfate 45g/L is made into liquid nutrient medium, pH1.80, after inoculation of medium bacterium, 36h is cultivated in inflation, obtains inoculum.
(2) arsenic mineral Bacterial Pre-oxidation: 1000g arsenic-containing gold concentrate is added in 4000mL inoculum, be made into the ore pulp that concentration is massfraction 20%, pack into leach in steel basin and carry out Bacterial Pre-oxidation.Preoxidation condition is: slurry pH 1.80,30 ℃ of temperature, aeration quantity 5.0L/L.min, stirring velocity are 500rpm.In solution, arsonium ion content reaches 12.97g/L, extends the reaction times, and arsenic content no longer increases, stopped reaction, and oxidization time is 7 days.Slurry filtration, washing, solid-liquid separation, obtains preoxidation slag 866g, and preoxidation slag is used for extracting gold, in slag, containing arsenic 0.36%, shows in ore that 94.33% arsenic enters solution.
(3) recovery of arsenic in solution: filtered liquid, washings merge and amount to 10L, and in solution, arsenic content is 5.18g/L, and regulating above-mentioned arsenic containing solution pH value with solid sodium hydroxide is 6.05, the Cu in solution
2+, Pd
2+, Zn
2+, Fe
3+form precipitation Deng metal ion with oxyhydroxide, filters and removes foreign ion.Under agitation condition, the amount that is 2: 1 by copper and arsenic mol ratio adds copper sulfate in filtrate, regulator solution pH value is 8.13, and reaction 1.5h, through precipitation, filter, washing, dry, obtain the thick level of cupric arsenite product 191g, containing arsenic 26.85%, show in solution that 99% arsenic enters the thick level of cupric arsenite product.From ore, the Bioleaching Rate of Sulphide Ores of arsenic is that 94.33% comprehensive recovery that calculates arsenic is 93.39%.It is 9.0 left and right that waste water after heavy arsenic regulates pH value with calcium oxide, further removes the foreign ion in solution, and it is 7.0 left and right that the waste water after calcium oxide removal of impurities is neutralized to pH value with sulfuric acid, and to remove the calcium ion in solution, the waste water after processing can qualified discharge.
Embodiment 2
In certain high arsenic golden ore concentrate hard to treat, containing arsenic 14.00%, gold grade is 41.5g/t ore, and granularity accounts for 92.30%, adopts steps of processing for-0.043mm:
(1) spawn culture: take acidithiobacillus ferrooxidans as ore leaching strain, with ammonium sulfate 5g/L, Repone K 0.1g/L, dipotassium hydrogen phosphate 0.5g/L, nitrocalcite 0.02g/L, ferrous sulfate 45g/L is made into liquid nutrient medium, pH1.80, after inoculation of medium bacterium, 36h is cultivated in inflation, obtains inoculum.
(2) arsenic mineral Bacterial Pre-oxidation: 500g arsenic-containing gold concentrate is added in 4500mL inoculum, be made into the ore pulp that concentration is massfraction 10%, pack into leach in steel basin and carry out Bacterial Pre-oxidation.Preoxidation condition is: slurry pH 1.80,30 ℃ of temperature, aeration quantity 5.0L/L.min, stirring velocity are 500rpm.In solution, arsonium ion content reaches 15.10g/L, extend the reaction times, arsenic content no longer increases, stopped reaction, and oxidization time is 7 days, slurry filtration, washing, solid-liquid separation, obtains preoxidation slag 421g, and preoxidation slag is used for extracting gold, in slag, containing arsenic 0.49%, show in ore that 97.06% arsenic enters solution.
(3) recovery of arsenic in solution: filtered liquid, washings merge and amount to 10 L, and in solution, arsenic content is 6.79g/L.With solid sodium hydroxide, regulating above-mentioned arsenic containing solution pH value is 6.15, the Cu in solution
2+, Pd
2+, Zn
2+, Fe
3+form precipitation Deng metal ion with oxyhydroxide, filters and removes foreign ion.Under agitation condition, the amount that is 2: 1 by copper and arsenic mol ratio adds copper sulfate in filtrate, regulator solution pH value is 8.07, and reaction 2.0h, through precipitation, filter, washing, dry, obtain the thick level of cupric arsenite product 262g, containing arsenic 25.63%, show in solution that 98.89% arsenic enters the thick level of cupric arsenite product.From ore, the Bioleaching Rate of Sulphide Ores of arsenic is that 97.06% comprehensive recovery that calculates arsenic is 95.98%.It is 9.0 left and right that waste water after heavy arsenic regulates pH value with calcium oxide, further removes the foreign ion in solution, and it is 7.0 left and right that the waste water after calcium oxide removal of impurities is neutralized to pH value with sulfuric acid, and to remove the calcium ion in solution, the waste water after processing can qualified discharge.
Claims (1)
1. from Gold Ore, extract a method for arsenic, it is characterized in that step is as follows:
(1) spawn culture: the acidithiobacillus ferrooxidans (Acidithiobacillus ferrooxidans) of take is ore leaching strain, with ammonium sulfate 2 ~ 6g/L, Repone K 0.1 ~ 0.2g/L, dipotassium hydrogen phosphate 0.1 ~ 1g/L, nitrocalcite 0.01 ~ 0.03g/L, ferrous sulfate 20 ~ 50g/L is made into liquid nutrient medium, pH1.5 ~ 2.0, after inoculated bacteria, 24 ~ 48h is cultivated in inflation, obtains inoculum;
(2) arsenic mineral Bacterial Pre-oxidation: granularity is added in inoculum for-0.043mm accounts for 75 ~ 95% arsenic-containing gold ore stone flour, be made into solids concentration massfraction and be 10 ~ 30% ore pulp, in Bacterial Pre-oxidation condition, be: slurry pH 1.5 ~ 2.0,25 ~ 45 ℃ of temperature, aeration quantity 2 ~ 8L/L.min, stirring velocity be 400 ~ 600rpm to ore pulp Bacterial Pre-oxidation, oxidization time 3 ~ 10 days; Regularly detect arsonium ion content in solution, when arsonium ion content tends towards stability in solution, end preoxidation, filter, washing ore pulp; From solution, reclaim arsenic, preoxidation slag is used for extracting gold from;
(3) recovery of arsenic in solution: regulating the pH value of above-mentioned arsenic containing solution with solid sodium hydroxide is 5.5 ~ 6.5, after filtration, by copper and arsenic mol ratio, it is 2: 1, in filtrate, add copper sulfate, regulator solution pH value is 8.0 ~ 8.5, stirring reaction 1 ~ 2h, through precipitation, filtration, washing, obtains cupric arsenite; With calcium oxide, regulating the filtrate pH value after precipitation cupric arsenite is 8.5 ~ 9.5, removes precipitation, and with sulfuric acid, being neutralized to pH value is 6.5 ~ 7.5 rear qualified discharges.
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| CN201310657811.4A CN103667695A (en) | 2013-12-09 | 2013-12-09 | Method for extracting arsenic from gold ore |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105087900A (en) * | 2015-05-25 | 2015-11-25 | 厦门紫金矿冶技术有限公司 | Dearsenification method of gold concentrates |
| CN105803194A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Method for arsenic bearing refractory gold ore microorganism pre-oxidation with high arsenic ion tolerance ore-leaching microorganism |
| CN105907961A (en) * | 2016-05-04 | 2016-08-31 | 长春黄金研究院 | Oxidation pretreatment method for strengthening arsenic containing gold concentrates through cooperation of oxidizing agent and catalyst |
| CN107254417A (en) * | 2017-04-27 | 2017-10-17 | 兰州博域生物科技有限责任公司 | A kind of preparation method of Biosorbent for heavy metals |
| CN114350947A (en) * | 2022-01-07 | 2022-04-15 | 有研资源环境技术研究院(北京)有限公司 | Special oxidizing bacteria and heap leaching pre-oxidation-gold extraction process for refractory gold ore organisms |
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| CN101168451A (en) * | 2006-10-25 | 2008-04-30 | 中南大学 | Method for preparing copper arsenite or copper arsenate by using arsenic-containing waste water |
| CN101333599A (en) * | 2008-04-30 | 2008-12-31 | 东北大学 | Cyanidation aurum-extracting method for preprocessing high-arsenic complex refractory gold ore by oxidation with arsenic resistant strains |
| CN101993835A (en) * | 2010-05-27 | 2011-03-30 | 威远川奇生工科技有限责任公司 | Arsenic-resistant bacteria and method for performing oxidation treatment on high-arsenic gold concentrate by using same |
| CN102337402A (en) * | 2011-10-26 | 2012-02-01 | 广州有色金属研究院 | Extraction method of gold from gold-containing sulfur ore concentrate |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
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Patent Citations (5)
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| CN101168451A (en) * | 2006-10-25 | 2008-04-30 | 中南大学 | Method for preparing copper arsenite or copper arsenate by using arsenic-containing waste water |
| CN101333599A (en) * | 2008-04-30 | 2008-12-31 | 东北大学 | Cyanidation aurum-extracting method for preprocessing high-arsenic complex refractory gold ore by oxidation with arsenic resistant strains |
| CN101993835A (en) * | 2010-05-27 | 2011-03-30 | 威远川奇生工科技有限责任公司 | Arsenic-resistant bacteria and method for performing oxidation treatment on high-arsenic gold concentrate by using same |
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| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803194A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Method for arsenic bearing refractory gold ore microorganism pre-oxidation with high arsenic ion tolerance ore-leaching microorganism |
| CN105803194B (en) * | 2014-12-30 | 2017-11-14 | 北京有色金属研究总院 | A kind of method that arsenic-bearing refractory gold ore microbe-preoxidation gold is carried out using high arsenic ion tolerance leaching microbacteria |
| CN105087900A (en) * | 2015-05-25 | 2015-11-25 | 厦门紫金矿冶技术有限公司 | Dearsenification method of gold concentrates |
| CN105907961A (en) * | 2016-05-04 | 2016-08-31 | 长春黄金研究院 | Oxidation pretreatment method for strengthening arsenic containing gold concentrates through cooperation of oxidizing agent and catalyst |
| CN107254417A (en) * | 2017-04-27 | 2017-10-17 | 兰州博域生物科技有限责任公司 | A kind of preparation method of Biosorbent for heavy metals |
| CN107254417B (en) * | 2017-04-27 | 2020-09-22 | 兰州大学 | Preparation method of heavy metal biological adsorbent |
| CN114350947A (en) * | 2022-01-07 | 2022-04-15 | 有研资源环境技术研究院(北京)有限公司 | Special oxidizing bacteria and heap leaching pre-oxidation-gold extraction process for refractory gold ore organisms |
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Application publication date: 20140326 |