CN102139919A - Method for reducing arsenic and lead in production of antimonous oxide by wet process - Google Patents
Method for reducing arsenic and lead in production of antimonous oxide by wet process Download PDFInfo
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- CN102139919A CN102139919A CN 201110041717 CN201110041717A CN102139919A CN 102139919 A CN102139919 A CN 102139919A CN 201110041717 CN201110041717 CN 201110041717 CN 201110041717 A CN201110041717 A CN 201110041717A CN 102139919 A CN102139919 A CN 102139919A
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Abstract
The invention discloses a method for reducing arsenic and lead which serve as products in the production of high-purity antimonous oxide by processing antimony sulfide ore concentrates, which comprises the following steps of: adding sodium thiosulfate into leached solution which is subjected to primary reduction to reduce arsenic, and precipitating for at least 2 hours, so that arsenic content in the solution is controlled to be within 30 ppm; heating vulcanizing filter liquor to the temperature of between 50 and 90 DEG C, introducing chlorine for oxidizing, precipitating for at least 2 hours, and cooling the solution, so that lead content in a liquid phase is reduced to 900 g/m<3>; and performing secondary reduction, hydrolyzing, neutralizing, removing lead by adding disodium edetate, and drying to prepare high-purity antimony oxide products of which the lead content and arsenic content are within the range of 10 ppm.
Description
Technical field
The invention belongs to the hydrometallurgy field, plumbous method falls in arsenic removal when relating to chloride-hydrolysis processing stibnite concentrate production high purity sb2o3.
Background technology
Metallic antimony uses seldom separately, and the alloy of metals such as all cpds of antimony and antimony and lead, tin, copper then has purposes widely.Fire retardant industry is consumption antimony field maximum in the world today, and the antimony consumption accounts for the 70%-75% of world's antimony total quantity consumed.Weisspiessglanz is a kind of good fire retarding synergist, can produce good flame from putting out effect with the halogenide acting in conjunction.Sb system fire retardant is widely used in plastics, electrical element and the chemical fibre textile.
Along with the extensively usefulness and the modern society of high molecular synthetic material are more and more higher to fire protection requirement, the consumption of fire retardant and weisspiessglanz also constantly increases thereupon.China is mainly based on outlet star metal, thick weisspiessglanz even antimony ore sand, and the antimony valency is subjected to the American-European control of main country of consumption, variation between every year even every month is all very big, therefore the research field of metallic antimony is widened in domestic appealing, the increasing weisspiessglanz is produced, walk deep processing and export, country gives encouragement from every side to these environmental protection antimony products simultaneously.
At present the technology of domestic production antimonous oxide mainly is divided into two kinds of pyrogenic process and wet methods.It is antimony slab that pyrogenic process is produced the antimonous oxide raw material, and under the pressure of the raising of environmental requirement both at home and abroad, low-concentration sulfur dioxide and arsenic alkali slag that its pyrogenic process is produced the generation of antimony slab process have brought very big pressure to environmental treatment.The wet production antimonous oxide has been avoided this environmental issue, and chemical index such as the arsenic of the antimonous oxide product of producing, lead all are starkly lower than pyrogenic process, satisfies the existing environmental requirement of country fully.
Summary of the invention
The objective of the invention is to produce on the basis of antimonous oxide, further reduce the content of arsenic in the product, plumbous chemical index in original wet chlorination-hydrolysis method, produce a kind of arsenic, lead content all at 10ppm with interior high purity sb2o3 product,
Satisfying domestic and international environmental requirement, this method is applied and truly feasible industrial.
The objective of the invention is to realize by following manner:
Reduce arsenic, plumbous method during a kind of wet production antimonous oxide, may further comprise the steps:
1) once reduction
The chloridizing leach solution of stibnite concentrate adds stibnite concentrate and once reduces;
2) Sulfothiorine removal of impurities
One time reduced liquid adds the Sulfothiorine removal of impurities, filters, and the filtrate precipitation is no less than 2 hours;
3) oxidation
Step 2) solution of post precipitation filters, and feeds chlorine oxidation in the filtrate, reaction to have elemental sulfur separate out and solution to be azarin brown, filter, precipitation is no less than 2 hours, filters, and is cooled to 10～40 ℃;
4) secondary reduction
The step 3) cooled solution is filtered, and filtrate adds the star metal powder and carries out secondary reduction;
Carry out secondary reduction by adding the star metal powder; With Sb excessive in the solution
5+Be reduced into Sb
3+(also comprising other high volence metal ion of reduction), its principal reaction equation is:
3Sb
5++2Sb＝5Sb
3+
Guarantee SbCl
3Contain Sb in the solution
3+Concentration reaches more than 99%, and the secondary reduction reaction times is about 3 hours.Carry out once more the reductive purpose and promptly utilize Sb
3+Under relatively low acidity, hydrolyzable becomes antimony oxychloride and other metal ion enters in the liquid phase.
5) hydrolysis, removal of impurities, neutralization
The secondary reduction posthydrolysis, the hydrolyzed product antimony oxychloride is by adding Sb
3+0.03～0.15 times disodium ethylene diamine tetraacetate removal of impurities of total input quality 3～5 hours adds the ammoniacal liquor neutralization, and the products obtained therefrom washing and drying gets final product.
Step 2) the adding quality of described Sulfothiorine is 0.8～1.4 times of arsenic mass content in reduced liquid; Reacted 2～5 hours.
Feed the excessive chlorine oxidation in the described filtrate of step 3); 50～90 ℃ of oxidizing reaction temperatures.
In the described hydrolytic process of step 5), the filtrate after the secondary reduction and the water volume ratio of adding are 1: 10; Stirred 20～100 minutes, precipitation 20～90min after-filtration promptly gets the hydrolyzed product antimony oxychloride, adopts pure water washing 20～60min again.
Antimony oxychloride after the washing adds water neutralization, the volume ratio of antimony oxychloride and water 1: 3～5.
After the removal of impurities, add the ammoniacal liquor of mass concentration 17% in the described step 5), the ammoniacal liquor add-on is 1: 3 with the ratio of antimony oxychloride quality, and endpoint pH is controlled at 8～10, filters the back and dries 20-60min with the pure water washing, and oven dry gets final product.
Principle of the present invention and advantage:
1, the arsenic in the solution exists with free trivalent arsenic ion, and Sulfothiorine adds, and the arsenic in its many sulfate ions and the solution produces complex reaction, the precipitation that forms reddish-brown enter slag mutually in, thereby reach the purpose of arsenic content in the reduction liquid phase; Reaction back solution inner suspension filter residue is a reddish-brown; The filtrate post precipitation, arsenic content can be reduced in the 30ppm in the solution.
2, feed chlorine and carry out oxidation, reaction end is that solution is that azarin is brown and have obviously visible elemental sulfur to separate out.Lead in the liquid phase by with chlorion reaction, generate the compound of lead chloride, lead chloride is unbound state when high temperature, post precipitation reduces the temperature in the solution, lead chloride then changes sedimentary form gradually into and enters slag and separate out in mutually.The filtrate post precipitation, lead content is lower than 900g/m
3Its purpose of process of cooling mainly is that impurity such as arsenic in the solution, lead, sulphur are separated out more completely, and temperature is low more, is beneficial to separating out of impurity more.
3, the cleaner disodium ethylene diamine tetraacetate adds in the solution, because sodium ion metallicity is strong, in liquid phase, be unbound state, make lead ion and ethylenediamine tetraacetic acid (EDTA) radical ion generation chelatropic reaction in the solution, form the stable free compound, in washing process, removed.
Description of drawings
Fig. 1 is a concrete process flow sheet of the present invention.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
The flow process of suitability for industrialized production of the present invention is as follows:
The a certain mineral resources major ingredient of table 1 content
| Sb％ | Pb％ | As％ | Bi％ | Cu％ | Au?g/t | SiO 2％ | H 2O％ |
| 36.38 | 0.67 | 0.25 | 0.0015 | 0.1 | 0.5 | 24.58 | 16.4 |
Chloridizing leach solution (the chlorination leaching method that adopts patent of invention CN 1041787A is leached in chlorination) the adding stibnite concentrate of above-mentioned-80 order stibnite concentrates is once reduced; Reduced liquid adds the Sulfothiorine removal of impurities, and the adding quality of Sulfothiorine is 0.8～1.4 times of arsenic mass content in reduced liquid; (Sulfothiorine is industrial rank, main content 99.96%) reaction 2-5 hour.Filter, the filtrate precipitation is no less than 2 hours.The solution of post precipitation filters, and feeds excessive chlorine oxidation, oxidizing reaction temperature 50-90 ℃ in the filtrate; Reaction to have elemental sulfur separate out and solution to be azarin brown, filter, precipitation is no less than 2 hours, filters, and is cooled to 10～40 ℃.Cooled solution is filtered, and filtrate adds star metal powder (below 0.5 millimeter) and carries out secondary reduction; Filtrate after the reaction adds the deionized water hydrolysis, and both volume ratios are 1: 10; Stirred 20-100 minute, and precipitated 20-90 minute after-filtration, promptly get antimony oxychloride, adopt pure water to wash 20-60min at least.Antimony oxychloride after the washing adds pure water neutralization, the volume ratio 1 of antimony oxychloride and water: 3-5.Allocate Sb into 2.5 tons of antimony oxychlorides again
3+The disodium ethylene diamine tetraacetate removal of impurities that concentration is 0.03～0.15 times 3-5 hour.The ammoniacal liquor that adds mass concentration 17% at last, the ammoniacal liquor add-on is 1: 3 with the ratio of antimony oxychloride quality, endpoint pH is controlled at 8～10, filters the back and dries 20-60min with the pure water washing, detects no white precipitate with Silver Nitrate and generates.100～200 ℃ of oven dry of baking oven get final product.
The quality product of carrying out explained hereafter by above-mentioned technical process in the workshop the results are shown in following table 2:
Table 2 workshop explained hereafter quality product result
Different cleaners of table 3 and consumption are to the influence of lead
Below be in the laboratory different condition for arsenic removal, plumbous influence.
Different Sulfothiorine consumptions are to removing the effect experiment of arsenic, its result such as table 4:
Table 4 Sulfothiorine consumption is to removing the influence of arsenic
The solution of getting the oxidizing reaction front and back has carried out lead content influence contrast assay, its result of laboratory test such as table 5:
The table 5 oxidation precipitation time is to the influence of lead content in the liquid phase
The add-on of table 6 disodium ethylene diamine tetraacetate is to the influence of product lead content
| Antimonous oxide weight g | Disodium ethylene diamine tetraacetate consumption g | Product lead content ppm |
| ?100 | 0.2 | 23 |
| ?100 | 0.3 | 15 |
| ?100 | 0.4 | 8 |
| ?100 | 0.5 | 9 |
| ?100 | 0.6 | 7 |
The corresponding laboratory of this mineral resources of table 7 quality product result of laboratory test
Claims (6)
1. reduce arsenic, plumbous method during a wet production antimonous oxide, it is characterized in that, may further comprise the steps:
1) once reduction
The chloridizing leach solution of stibnite concentrate adds stibnite concentrate and once reduces;
2) Sulfothiorine removal of impurities
One time reduced liquid adds the Sulfothiorine removal of impurities, filters, and the filtrate precipitation is no less than 2 hours;
3) oxidation
Step 2) solution of post precipitation filters, and feeds chlorine oxidation in the filtrate, reaction to have elemental sulfur separate out and solution to be azarin brown, filter, precipitation is no less than 2 hours, filters, and is cooled to 10～40 ℃;
4) secondary reduction
The step 3) cooled solution is filtered, and filtrate adds the star metal powder and carries out secondary reduction;
5) hydrolysis, removal of impurities, neutralization
The secondary reduction posthydrolysis, the hydrolyzed product antimony oxychloride is by adding Sb
3+0.03～0.15 times disodium ethylene diamine tetraacetate removal of impurities of total input quality 3～5 hours adds the ammoniacal liquor neutralization, and the products obtained therefrom washing and drying gets final product.
2. reducing arsenic, plumbous method during a kind of wet production antimonous oxide according to claim 1, it is characterized in that step 2) the adding quality of described Sulfothiorine is 0.8～1.4 times of arsenic mass content in reduced liquid; Reacted 2～5 hours.
3. reduce arsenic, plumbous method during a kind of wet production antimonous oxide according to claim 1, it is characterized in that, feed the excessive chlorine oxidation in the described filtrate of step 3); 50～90 ℃ of oxidizing reaction temperatures.
4. reduce arsenic, plumbous method during a kind of wet production antimonous oxide according to claim 1, it is characterized in that in the described hydrolytic process of step 5), the filtrate after the secondary reduction and the water volume ratio of adding are 1: 10; Stirred 20～100 minutes, precipitation 20～90min after-filtration promptly gets the hydrolyzed product antimony oxychloride, adopts pure water washing 20～60min again.
5. reduce arsenic, plumbous method during a kind of wet production antimonous oxide according to claim 4, it is characterized in that the antimony oxychloride after the washing adds water neutralization, the volume ratio of antimony oxychloride and water 1: 3～5.
6. reduce arsenic, plumbous method during a kind of wet production antimonous oxide according to claim 1, it is characterized in that, in the described step 5) after the removal of impurities, the ammoniacal liquor that adds mass concentration 17%, the ammoniacal liquor add-on is 1: 3 with the ratio of antimony oxychloride quality, endpoint pH is controlled at 8～10, filters the back and dries 20-60min with the pure water washing, and oven dry gets final product.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976408A (en) * | 2012-09-19 | 2013-03-20 | 湖南辰州矿业股份有限公司 | Method for producing orthorhombic crystal form antimony trioxide through wet method |
| CN102978397A (en) * | 2012-10-12 | 2013-03-20 | 金川集团股份有限公司 | Removal method of arsenic from arsenic-containing waste liquid with high acidity |
| CN102976407A (en) * | 2012-09-19 | 2013-03-20 | 湖南辰州矿业股份有限公司 | Method for increasing diantimony trioxide particle size during wet production process of diantimony trioxide |
| CN103397206A (en) * | 2013-07-10 | 2013-11-20 | 湖南辰州矿业股份有限公司 | Method for wet processing of antimony trioxide powder with high arsenic content |
| CN103849782A (en) * | 2012-11-28 | 2014-06-11 | 湖南宇腾有色金属股份有限公司 | High-pressure alkaline leaching arsenic-removal method for high-arsenic antimony white powder |
| CN104944469A (en) * | 2015-07-17 | 2015-09-30 | 湖南辰州矿业有限责任公司 | Technique for producing high-purity antimonous oxide by processing stibnite concentrate through wet method |
| CN106381385A (en) * | 2016-09-20 | 2017-02-08 | 湖南辰州矿业有限责任公司 | Method for treatment of antimony sulfide concentrates through wet method short process |
| CN107338272A (en) * | 2017-06-17 | 2017-11-10 | 常州杰轩纺织科技有限公司 | A kind of recycling processing method of arsenic-containing waste residue |
| CN108793249A (en) * | 2018-08-31 | 2018-11-13 | 锡矿山闪星锑业有限责任公司 | A method of from cupric, lead low-grade antimony ore in extract antimony oxide |
| CN109706331A (en) * | 2019-03-01 | 2019-05-03 | 赣州有色冶金研究所 | A kind of method of tungsten concentrate dearsenification |
| CN111679031A (en) * | 2020-04-28 | 2020-09-18 | 西北矿冶研究院 | Method for measuring antimony in crude lead by precipitation separation-carbon reduction cerium sulfate volumetric method |
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| CN85107329A (en) * | 1985-09-29 | 1986-07-09 | 中南工业大学 | Antimony sulfide ore " chlorination-hydrolysis method " is produced stibium trioxide |
| JPS63248724A (en) * | 1987-04-03 | 1988-10-17 | Mitsubishi Metal Corp | Production of fibrous antimony oxide |
| CN1041787A (en) * | 1988-10-11 | 1990-05-02 | 中南工业大学 | The treatment process of antimony sulfide ore of high lead and arsenic content |
| CN1072392A (en) * | 1992-12-12 | 1993-05-26 | 北京航空材料研究所 | The preparation method of cubic crystal antimony trioxide |
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2011
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Patent Citations (4)
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| CN85107329A (en) * | 1985-09-29 | 1986-07-09 | 中南工业大学 | Antimony sulfide ore " chlorination-hydrolysis method " is produced stibium trioxide |
| JPS63248724A (en) * | 1987-04-03 | 1988-10-17 | Mitsubishi Metal Corp | Production of fibrous antimony oxide |
| CN1041787A (en) * | 1988-10-11 | 1990-05-02 | 中南工业大学 | The treatment process of antimony sulfide ore of high lead and arsenic content |
| CN1072392A (en) * | 1992-12-12 | 1993-05-26 | 北京航空材料研究所 | The preparation method of cubic crystal antimony trioxide |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976407A (en) * | 2012-09-19 | 2013-03-20 | 湖南辰州矿业股份有限公司 | Method for increasing diantimony trioxide particle size during wet production process of diantimony trioxide |
| CN102976408A (en) * | 2012-09-19 | 2013-03-20 | 湖南辰州矿业股份有限公司 | Method for producing orthorhombic crystal form antimony trioxide through wet method |
| CN102978397A (en) * | 2012-10-12 | 2013-03-20 | 金川集团股份有限公司 | Removal method of arsenic from arsenic-containing waste liquid with high acidity |
| CN103849782B (en) * | 2012-11-28 | 2014-12-10 | 湖南宇腾有色金属股份有限公司 | High-pressure alkaline leaching arsenic-removal method for high-arsenic antimony white powder |
| CN103849782A (en) * | 2012-11-28 | 2014-06-11 | 湖南宇腾有色金属股份有限公司 | High-pressure alkaline leaching arsenic-removal method for high-arsenic antimony white powder |
| CN103397206B (en) * | 2013-07-10 | 2015-02-18 | 湖南辰州矿业股份有限公司 | Method for wet processing of antimony trioxide powder with high arsenic content |
| CN103397206A (en) * | 2013-07-10 | 2013-11-20 | 湖南辰州矿业股份有限公司 | Method for wet processing of antimony trioxide powder with high arsenic content |
| CN104944469A (en) * | 2015-07-17 | 2015-09-30 | 湖南辰州矿业有限责任公司 | Technique for producing high-purity antimonous oxide by processing stibnite concentrate through wet method |
| CN106381385A (en) * | 2016-09-20 | 2017-02-08 | 湖南辰州矿业有限责任公司 | Method for treatment of antimony sulfide concentrates through wet method short process |
| CN107338272A (en) * | 2017-06-17 | 2017-11-10 | 常州杰轩纺织科技有限公司 | A kind of recycling processing method of arsenic-containing waste residue |
| CN108793249A (en) * | 2018-08-31 | 2018-11-13 | 锡矿山闪星锑业有限责任公司 | A method of from cupric, lead low-grade antimony ore in extract antimony oxide |
| CN109706331A (en) * | 2019-03-01 | 2019-05-03 | 赣州有色冶金研究所 | A kind of method of tungsten concentrate dearsenification |
| CN111679031A (en) * | 2020-04-28 | 2020-09-18 | 西北矿冶研究院 | Method for measuring antimony in crude lead by precipitation separation-carbon reduction cerium sulfate volumetric method |
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Address after: 419607, Huaihua County, Hunan City, Yuanling Province Patentee after: Hunan gold Limited by Share Ltd. Address before: 419607, Huaihua County, Hunan City, Yuanling Province Patentee before: Hunan Chenzhou Mining Group Co.,Ltd. |
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Effective date of registration: 20151218 Address after: 419607, Hunan, Huaihua province Yuanling County town of Wo Wo Village Patentee after: HUNAN CHENZHOU MINING INDUSTRY Co.,Ltd. Address before: 419607, Huaihua County, Hunan City, Yuanling Province Patentee before: Hunan gold Limited by Share Ltd. |