CN104099480B - A kind of slag bismuth oxide prepares the method for bismuth electrolytic solution - Google Patents

A kind of slag bismuth oxide prepares the method for bismuth electrolytic solution Download PDF

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CN104099480B
CN104099480B CN201410388634.9A CN201410388634A CN104099480B CN 104099480 B CN104099480 B CN 104099480B CN 201410388634 A CN201410388634 A CN 201410388634A CN 104099480 B CN104099480 B CN 104099480B
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bismuth
solution
slag
sulfuric acid
copper
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CN104099480A (en
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陈万天
宋国生
陈知勇
瞿继育
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JIANGXI LONGTIANYONG NONFERROUS METALS Co Ltd
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Abstract

The invention provides a kind of method that slag bismuth oxide prepares bismuth electrolytic solution, it is characterized in that: levigate slag bismuth oxide filters after silicofluoric acid system leaches, leached mud returns silver converter converting process, first in leach liquor, lead powder is added with the copper in substitutional solution, after copper removal, liquid adds retrieval of sulfuric acid lead, and after sulfuric acid depositing purification, gained solution is qualified bismuth electrolytic solution.The present invention adopts silicofluoric acid system to leach, and realizes bismuth lead bronze and is separated with silver-colored, and not only precious metal overstocks few, and metal leaching rate is high.

Description

A kind of slag bismuth oxide prepares the method for bismuth electrolytic solution
Technical field
The present invention relates to hydrometallurgy process in field of metallurgy, particularly effectively prepare the Wet-process metallurgy method of bismuth electrolytic solution with slag bismuth oxide.
Background technology
The thinking that the pyrogenic attack technique of the copper-lead anode sludge adopts adopts retailoring and oxidation refining two processes to remove base metal, output is enriched 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 metal, divide three phases oxidation, first be antimony, arsenic and plumbous oxidation enter flue dust, next is blown into air to make bismuth and plumbous oxidation form slag bismuth oxide, finally add oxygenant to make copper, selenium and tellurium be oxidized output tellurium slag, main containing bismuth, lead and copper in slag bismuth oxide, and antimony and arsenic on a small quantity.
About the technique study extracting bismuth in slag bismuth oxide is a lot, normally adopts the thick bismuth of the method enrichment such as pyrometallurgical smelting or dissolving with hydrochloric acid output, and then utilize pyrorefining or the qualified bismuth ingot of electrorefining output.
Pyrometallurgical smelting method is then melting in reverberatory furnace or converter after being mixed with flux by slag bismuth oxide, the thick bismuth of direct output, the method is suitability for industrialized production, non-wastewater discharge, but has 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 then directly dissolve bismuth in sulfuric acid and hydrochloric acid system, plumbous and silver enters leached mud with lead sulfate and silver chloride state respectively, bismuth-containing solution hydrolysis output bismuth slag, bismuth slag is again through the thick bismuth of retailoring output, the method can accomplish the synthetical 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 pyrorefining and electrorefining two kinds, 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, wherein to whole process influence maximum be add zinc to eliminate silver and chlorinating scraping lead two operations, these two operations not only length consuming time, and metal recovery rate can be caused significantly to reduce 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 bismuth-containing many metalliferous materials, 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 one and can effectively prepare bismuth electrolytic solution and the free of contamination Wet-process metallurgy method of process.
The present invention be achieve the above object adopt technical scheme be: levigate slag bismuth oxide silicofluoric acid system leach after filter, leached mud returns silver converter converting process, first in leach liquor, lead powder is added with the copper in substitutional solution, after copper removal, liquid adds retrieval of sulfuric acid lead, and after purification, liquid is qualified bismuth electrolytic solution.
Concrete technological process and processing parameter as follows:
1 broken and fine grinding
Slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 44 ~ 220 μm.
2 silicofluoric acid leach
Slag bismuth oxide after fine grinding leaches in silicate fluoride solution, compound concentration is 280 ~ 560g/L silicate fluoride solution, the slag bismuth oxide after fine grinding is added by liquid-solid ratio 3 ~ 6: 1, control temperature of reaction 40 ~ 80 DEG C and stirring velocity 200 ~ 250r/min, filter after reaction 1 ~ 6h, return converter after leached mud washing, the chemical reaction occurred 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, copper removal is purified
With the copper in lead powder displacement silicofluoric acid leach liquor, add the lead powder of copper mass content 3.3 ~ 3.5 times in leach liquor, reaction 1 ~ 2h at temperature 40 ~ 80 DEG C and stirring velocity 150 ~ 250r/min condition, 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 solution temperature 40 ~ 75 DEG C and stirring velocity 150 ~ 250r/min, after copper removal, in liquid, add the sulfuric acid of plumbous mass content 0.60 ~ 1.60 times in solution, filter 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 the slag bismuth oxide processing 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, compared with the method for traditional extraction bismuth, has following advantage:
1, adopt slag bismuth oxide directly to prepare bismuth electrolytic solution, achieve 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 and be separated with silver-colored, not only precious metal overstocks few, and metal leaching rate is high; 3, solution circulated utilize, 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 present invention process schematic flow sheet.
Embodiment
Technical process of the present invention as shown in Figure 1, comprises step: S1 is broken with fine grinding, S2 silicofluoric acid leach, S3 purifies copper removal, S4 sulfuric acid depositing, describes the present invention in detail below in conjunction with embodiment.
embodiment 1
Block slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 150 μm, and its main component is (%) by weight percentage: Bi33.0, Pb12.0, Cu2.8, Ag0.85 and Sb1.2, 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, add the bismuth oxide powder 600g of mentioned component, keep temperature 60 C and stirring velocity 200r/min, filter after reaction 3h, 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 solution temperature 60 DEG C and 250r/min, adds 60g lead powder and filter after reacting 2h, replacement slag washing post-drying, replacement slag weight 20.4g.After copper removal, liquid adds sulfuric acid precipitation lead, keeps solution temperature 60 DEG C and 150r/min, adds 50ml sulfuric acid and filter after reacting 1h, and it is 192.5g that sulfuric acid lead skim dries rear weight.
embodiment 2
Block slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 44 μm.Compound concentration is the silicate fluoride solution 3600ml of 400g/L, adds the bismuth oxide powder 600g of mentioned component, keeps temperature 80 DEG C and stirring velocity 250r/min, filters, obtain silicofluoric acid leach liquor after reaction 6h.Add the lead powder displacement copper of copper mass content 3.3 times to silicofluoric acid leach liquor, keep solution temperature 80 DEG C and 250r/min, and filter after reacting 1h, replacement slag washing post-drying.After copper removal, liquid adds the sulfuric acid of plumbous mass content 1.60 times, filters, keep solution temperature 75 DEG C and 150r/min after reaction 1h, adds 50ml sulfuric acid and filter after reacting 2h to obtain bismuth electrolytic solution.
embodiment 3
Block slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 220 μm.Compound concentration is the silicate fluoride solution 1800ml of 560g/L, adds the bismuth oxide powder 600g of mentioned component, keeps temperature 40 DEG C and stirring velocity 200r/min, filters, obtain silicofluoric acid leach liquor after reaction 1h.Add the lead powder displacement copper of copper mass content 3.5 times to silicofluoric acid leach liquor, keep solution temperature 40 DEG C and 150r/min, and filter after reacting 2h, replacement slag washing post-drying.After copper removal, liquid adds the sulfuric acid of plumbous mass content 0.60 times, filters, keep solution temperature 40 DEG C and 250r/min after reaction 1h, adds 50ml sulfuric acid and filter after reacting 1h to obtain bismuth electrolytic solution.

Claims (1)

1. prepare the method for bismuth electrolytic solution with slag bismuth oxide for one kind, levigate slag bismuth oxide is filtered after silicofluoric acid system leaches, leached mud returns silver converter converting process, lead powder is added with the copper in substitutional solution in leach liquor, after copper removal, liquid adds retrieval of sulfuric acid lead, after sulfuric acid depositing purification, gained solution is qualified bismuth electrolytic solution, it is characterized in that technological process is as follows:
1) broken and fine grinding: slag bismuth oxide is broken and be finely ground to granularity 100% and cross the sieve that aperture is 44 ~ 220 μm;
2) silicofluoric acid leaches: the slag bismuth oxide after fine grinding leaches in silicate fluoride solution; compound concentration is 280 ~ 560g/L silicate fluoride solution; add the slag bismuth oxide after fine grinding by liquid-solid ratio 3 ~ 6: 1, control temperature of reaction 40 ~ 80 DEG C and stirring velocity 200 ~ 250r/min, filter after reaction 1 ~ 6h;
3) copper removal is purified: with the copper in lead powder displacement silicofluoric acid leach liquor, in leach liquor, add the lead powder of copper mass content 3.3 ~ 3.5 times, reaction 1 ~ 2h at temperature 40 ~ 80 DEG C and stirring velocity 150 ~ 250r/min condition;
4) sulfuric acid depositing: with the lead in liquid after sulfuric acid precipitation copper removal, keep solution temperature 40 ~ 75 DEG C and stirring velocity 150 ~ 250r/min, after copper removal, in liquid, add the sulfuric acid of plumbous mass content 0.60 ~ 1.60 times in solution, filter after reaction 1 ~ 2h and obtain qualified bismuth electrolytic solution.
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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
CN108277345B (en) * 2018-01-29 2019-04-12 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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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Denomination of invention: Method for preparing bismuth electrolyte with bismuth oxide slag

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