CN104099480A - Method for preparing bismuth electrolyte with bismuth oxide slag - Google Patents
Method for preparing bismuth electrolyte with bismuth oxide slag Download PDFInfo
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- CN104099480A CN104099480A CN201410388634.9A CN201410388634A CN104099480A CN 104099480 A CN104099480 A CN 104099480A CN 201410388634 A CN201410388634 A CN 201410388634A CN 104099480 A CN104099480 A CN 104099480A
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- bismuth
- solution
- slag
- copper
- bismuth oxide
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Abstract
The invention provides a method for preparing bismuth electrolyte with bismuth oxide slag. The method is characterized by comprising the following steps: leaching fine-grained bismuth oxide slag in a fluosilicic acid system, and filtering; returning leaching slag back into a silver revolving furnace for blowing; adding lead powder into leach liquor to replace copper in a solution; adding sulfuric acid into the copper-removed solution to recover lead; precipitating lead in sulfuric acid for purifying to obtain a solution which is qualified bismuth electrolyte. By leaching through the fluosilicic acid system, separation of bismuth-lead-copper and silver is realized, piling of precious metals is reduced, and the metal leaching rate is high.
Description
Technical field
The present invention relates to hydrometallurgy process in field of metallurgy, particularly effectively with slag bismuth oxide, prepare the Wet-process metallurgy method of bismuth electrolytic solution.
Background technology
The thinking of the pyrogenic attack process using of the copper-lead anode sludge is to adopt retailoring and two processes of oxidation refining to remove base metal, output enrichment the electrum of precious metal, wherein, the oxidation refining process of precious metals containing lead is different according to the oxidation complexity of various foreign metals, divide three phases oxidation, first be that antimony, arsenic and plumbous oxidation enter flue dust, next is to be blown into air to make bismuth and plumbous oxidation form slag bismuth oxide, finally to add oxygenant to make copper, selenium and tellurium oxidation output tellurium slag, in slag bismuth oxide, mainly contain bismuth, lead and copper, and a small amount of antimony and arsenic.
The method research of extracting bismuth in relevant slag bismuth oxide is a lot, normally adopts the thick bismuths of method enrichment output such as pyrometallurgical smelting or dissolving with hydrochloric acid, and then utilizes pyrorefining or the qualified bismuth ingot of electrorefining output.
Pyrometallurgical smelting method is melting in reverberatory furnace or converter after slag bismuth oxide is mixed with flux, the direct thick bismuth of output, the method is suitability for industrialized production, non-wastewater discharge, but have that metal recovery rate is low, technical process is long, processing power is low, cost is high and the shortcoming such as environmental pollution is serious.Dissolving with hydrochloric acid is in sulfuric acid and hydrochloric acid system, directly to dissolve bismuth, plumbous and silver enters leached mud with lead sulfate and silver chloride state respectively, bismuth-containing solution hydrolysis output bismuth slag, bismuth slag passes through the thick bismuth of retailoring output again, the method can be accomplished the comprehensive recovery of valuable metal, but still has that metal recovery rate is low, processing cost is high and the shortcoming such as wastewater flow rate is large.
The refining of thick bismuth mainly comprises two kinds of pyrorefining and electrorefinings, fire refining process mainly comprises operations such as adding sulphur copper removal, oxidation arsenic removal antimony, basic refining detin, add zinc to eliminate silver and chlorinating scraping lead zinc, to whole process influence maximum, be wherein add zinc to eliminate silver and two operations of chlorinating scraping lead, these two operations are length consuming time not only, and can cause that metal recovery rate significantly reduces and problem of environmental pollution.Electrorefining mainly comprises three kinds of systems such as muriate, silicofluoric acid and fused salt, wherein muriate and silicofluoric acid system are widely used in industrial production, the electrolytic solution of chloride system is by hydrochloric acid and bismuth chloride solution composition, the electrolytic solution of silicofluoric acid system is by silicofluoric acid and the solution composition of silicofluoric acid bismuth, and electrolytic smelting method has the advantages such as energy consumption is low, simple to operate, constant product quality.
(1. bear moral is strong, Xiao Jine. from silver smelting oxidation sludge, reclaim the production practice of bismuth, precious metal, 2005,26 (2): 16 ~ 21. 2. Wang Li fruits. bismuth is metallurgical. Beijing, metallurgical industry press, 1986. 3. Wang Zhixiongs, Wu Zuxiang, Dai Yanping. the technique of comprehensive extraction of valent metal from the many metalliferous materials of bismuth-containing, Chinese patent, ZL200710034666.9, on February 18th, 2009).
Summary of the invention
In order to overcome the deficiency of traditional bismuth preparation method of electrolyte, the invention provides and a kind ofly can effectively prepare bismuth electrolytic solution and the free of contamination Wet-process metallurgy method of process.
The present invention is that the technical scheme adopting that achieves the above object is: levigate slag bismuth oxide filters after silicofluoric acid system leaches, leached mud returns to silver and bessemerizes process, first in leach liquor, add lead powder with the copper in substitutional solution, after copper removal, liquid adds retrieval of sulfuric acid plumbous, and after purifying, liquid is qualified bismuth electrolytic solution.
Concrete technological process and processing parameter are as follows:
1 fragmentation and fine grinding
Slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 44～220um.
2 silicofluoric acid leach
Slag bismuth oxide after fine grinding leaches in silicate fluoride solution, compound concentration is 280～560 g/L silicate fluoride solutions, by liquid-solid ratio 3～6: 1 adds the slag bismuth oxide after fine grinding, control 40～80 ℃ of temperature of reaction and stirring velocity 200～250r/min, after reaction 1～6h, filter, after leached mud washing, return to converter, the chemical reaction occurring in leaching process is as follows:
Bi
2O
3+3H
2SiF
6=Bi
2(SiF
6)
3+3H
2O （1）
MeO+H
2siF
6=MeSiF
6+ H
2o (Me is Cu, Pb) (2).
3, purify copper removal
With the copper in lead powder displacement silicofluoric acid leach liquor, the lead powder to adding 3.3～3.5 times of copper mass content in leach liquor reacts 1～2h under 40～80 ℃ of temperature and stirring velocity 150～250r/min condition, and the chemical reaction of generation is:
CuSiF
6+Pb= PbSiF
6+Cu↓ （3）。
4, sulfuric acid depositing
With the lead in liquid after sulfuric acid precipitation copper removal, keep 40～75 ℃ of solution temperatures and stirring velocity 150～250r/min, the sulfuric acid to adding 0.60～1.60 times of plumbous mass content in solution in liquid after copper removal, filters after reaction 1～2h, output sulfuric acid lead skim, the chemical reaction of generation is:
PbSiF
6+H
2SO
4= H
2SiF
6+PbSO
4↓ （4）
Described silicofluoric acid, lead powder and sulfuric acid are technical grade reagent.
The present invention is applicable to process the slag bismuth oxide of copper-lead anode sludge pyrometallurgical smelting process output, and its main component scope is (%) by weight percentage: Bi15.0～45.0, Pb10.2～20.0, Cu0.5～5.0, Ag0.10～5.0 and Sb0.2～4.5.
The present invention compares with the method for traditional extraction bismuth, has following advantage:
1, adopt slag bismuth oxide directly to prepare bismuth electrolytic solution, realized the comprehensive utilization of valuable metal, technical process is short, metal recovery rate is high; 2, adopt silicofluoric acid system to leach, realize bismuth lead bronze with silver-colored separated, not only precious metal overstocks less, and metal leaching rate is high; 3, solution circulated utilization, reagent consumption less, simple to operate; 4, labour intensity of the present invention is low, the treatment time is short, cost is low.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Technical process of the present invention as shown in Figure 1, comprises step: S1 is broken purifies copper removal, S4 sulfuric acid depositing with fine grinding, the leaching of S2 silicofluoric acid, S3, below in conjunction with embodiment, describes the present invention in detail.
embodiment 1
By block slag bismuth oxide, with broken and be finely ground to granularity 100% and cross the sieve that aperture is 150um, its main component is (%): Bi33.0, Pb12.0, Cu2.8, Ag0.85 and Sb1.2 by weight percentage, and all the other are O; Silicofluoric acid is technical grade reagent, silicofluoric acid content 40%, and lead powder and sulfuric acid are technical grade reagent.
Compound concentration is the silicate fluoride solution 1800ml of 280g/L, the bismuth oxide powder 600g that adds mentioned component, keep temperature 60 C and stirring velocity 200r/min, after reaction 3h, filter, leach liquor volume 1750ml, its main component is (g/L): Bi118.2, Pb40.8, Cu9.72 and Sb4.28, the heavy 60.5g of leached mud washing post-drying.
Silicofluoric acid leach liquor adds lead powder displacement copper, keeps 60 ℃ of solution temperatures and 250r/min, filters replacement slag washing post-drying, replacement slag weight 20.4g after adding 60g lead powder and reacting 2h.After copper removal, liquid adds sulfuric acid precipitation plumbous, keeps 60 ℃ of solution temperatures and 150r/min, after adding 50ml sulfuric acid and reacting 1h, filters, and it is 192.5g that sulfuric acid lead skim is dried rear weight.
embodiment 2
By block slag bismuth oxide with broken and be finely ground to granularity 100% and cross the sieve that aperture is 44um.Compound concentration is the silicate fluoride solution 3600ml of 400g/L, adds the bismuth oxide powder 600g of mentioned component, keeps 80 ℃ of temperature and stirring velocity 250r/min, after reaction 6h, filters, and obtains silicofluoric acid leach liquor.The lead powder displacement copper that adds 3.3 times of copper mass content to silicofluoric acid leach liquor, keeps 80 ℃ of solution temperatures and 250r/min, and filters after reacting 1h, replacement slag washing post-drying.After copper removal, liquid adds the sulfuric acid of 1.60 times of plumbous mass content, after reaction 1h, filters, and keeps 75 ℃ of solution temperatures and 150r/min, after adding 50ml sulfuric acid and reacting 2h, filters and obtains bismuth electrolytic solution.
embodiment 3
By block slag bismuth oxide with broken and be finely ground to granularity 100% and cross the sieve that aperture is 220um.Compound concentration is the silicate fluoride solution 1800ml of 560g/L, adds the bismuth oxide powder 600g of mentioned component, keeps 40 ℃ of temperature and stirring velocity 200r/min, after reaction 1h, filters, and obtains silicofluoric acid leach liquor.The lead powder displacement copper that adds 3.5 times of copper mass content to silicofluoric acid leach liquor, keeps 40 ℃ of solution temperatures and 150r/min, and filters after reacting 2h, replacement slag washing post-drying.After copper removal, liquid adds the sulfuric acid of 0.60 times of plumbous mass content, after reaction 1h, filters, and keeps 40 ℃ of solution temperatures and 250r/min, after adding 50ml sulfuric acid and reacting 1h, filters and obtains bismuth electrolytic solution.
Claims (2)
1. a method of preparing bismuth electrolytic solution with slag bismuth oxide, it is characterized in that: levigate slag bismuth oxide filters after silicofluoric acid system leaches, leached mud returns to silver and bessemerizes process, first in leach liquor, add lead powder with the copper in substitutional solution, after copper removal, liquid adds retrieval of sulfuric acid plumbous, and after sulfuric acid depositing purifies, gained solution is qualified bismuth electrolytic solution.
2. the method for preparing bismuth electrolytic solution with slag bismuth oxide according to claim 1, is characterized in that technological process is as follows:
(1) fragmentation and fine grinding: slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 44～220um;
(2) silicofluoric acid leaches: the slag bismuth oxide after fine grinding leaches in silicate fluoride solution; compound concentration is 280～560 g/L silicate fluoride solutions; by liquid-solid ratio 3～6: 1 adds the slag bismuth oxide after fine grinding; control 40～80 ℃ of temperature of reaction and stirring velocity 200～250r/min, after reaction 1～6h, filter;
(3) purify copper removal: with the copper in lead powder displacement silicofluoric acid leach liquor, the lead powder to adding 3.3～3.5 times of copper mass content in leach liquor reacts 1～2h under 40～80 ℃ of temperature and stirring velocity 150～250r/min condition;
(4) sulfuric acid depositing: with the lead in liquid after sulfuric acid precipitation copper removal, keep 40～75 ℃ of solution temperatures and stirring velocity 150～250r/min, sulfuric acid to adding 0.60～1.60 times of plumbous mass content in solution in liquid after copper removal, filters and obtains qualified bismuth electrolytic solution after reaction 1～2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048665A (en) * | 2017-11-30 | 2018-05-18 | 安徽省恒伟铋业有限公司 | A kind of process from Copper making fume recovery bismuth |
| CN108277345A (en) * | 2018-01-29 | 2018-07-13 | 昆明理工大学 | A method of the copper removal cadmium from zinc sulfate leaching liquid |
| CN111270267A (en) * | 2020-02-11 | 2020-06-12 | 云南驰宏资源综合利用有限公司 | Method for supplementing lead ions of lead electrolyte by using lead plaster of waste lead-acid storage battery |
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| CN1415785A (en) * | 2002-10-22 | 2003-05-07 | 郴州金旺实业有限公司 | Technique for electrolyzing slurry of fluosilicic acid in bismuth mine |
| CN101029353A (en) * | 2007-03-28 | 2007-09-05 | 湖南金旺实业有限公司 | Comprehensive extraction of valent metal from bismuth-containing polymetallic material |
| CN101245471A (en) * | 2008-03-07 | 2008-08-20 | 湖南昭山冶金化工有限公司 | Method for producing bismuth and enriched silver from high-silver bismuth alloy |
| CN103397180A (en) * | 2013-08-07 | 2013-11-20 | 江西铜业股份有限公司 | Method for recovering tellurium, bismuth, antimony, and copper from complex material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1415785A (en) * | 2002-10-22 | 2003-05-07 | 郴州金旺实业有限公司 | Technique for electrolyzing slurry of fluosilicic acid in bismuth mine |
| CN101029353A (en) * | 2007-03-28 | 2007-09-05 | 湖南金旺实业有限公司 | Comprehensive extraction of valent metal from bismuth-containing polymetallic material |
| CN101245471A (en) * | 2008-03-07 | 2008-08-20 | 湖南昭山冶金化工有限公司 | Method for producing bismuth and enriched silver from high-silver bismuth alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048665A (en) * | 2017-11-30 | 2018-05-18 | 安徽省恒伟铋业有限公司 | A kind of process from Copper making fume recovery bismuth |
| CN108277345A (en) * | 2018-01-29 | 2018-07-13 | 昆明理工大学 | A method of the copper removal cadmium from zinc sulfate leaching liquid |
| CN111270267A (en) * | 2020-02-11 | 2020-06-12 | 云南驰宏资源综合利用有限公司 | Method for supplementing lead ions of lead electrolyte by using lead plaster of waste lead-acid storage battery |
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Denomination of invention: Method for preparing bismuth electrolyte with bismuth oxide slag Effective date of registration: 20191030 Granted publication date: 20160330 Pledgee: Yongfeng sub branch of Jiujiang Bank Co.,Ltd. Pledgor: JIANGXI LONGTIANONG NONFERROUS METAL CO.,LTD. Registration number: Y2019990000442 |
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Date of cancellation: 20220802 Granted publication date: 20160330 Pledgee: Yongfeng sub branch of Jiujiang Bank Co.,Ltd. Pledgor: JIANGXI LONGTIANONG NONFERROUS METAL CO.,LTD. Registration number: Y2019990000442 |