CN102304621A - Process for separating out Sn, Bi, Cu and Zn from Sn-Bi waste material - Google Patents
Process for separating out Sn, Bi, Cu and Zn from Sn-Bi waste material Download PDFInfo
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- CN102304621A CN102304621A CN201110297150A CN201110297150A CN102304621A CN 102304621 A CN102304621 A CN 102304621A CN 201110297150 A CN201110297150 A CN 201110297150A CN 201110297150 A CN201110297150 A CN 201110297150A CN 102304621 A CN102304621 A CN 102304621A
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Abstract
The invention relates to a process for separating out Sn, Bi, Cu and Zn from a Sn-Bi waste material and belongs to the field of nonferrous metal element separation from solid waste materials by a wet method. The process is characterized in that the solid waste material generated by recovering Sn-Bi alloy electroplating waste liquid is called the Sn-Bi waste material, the Sn-Bi waste material comprises the following typical components by weight percent: 37.72% of H2O, 14.7% of Bi, 1.56% of Cu, 38.29% of Sn, 1.35% of Zn and 6.38% of O, and the four elements namely Sn, Bi, Cu and Zn are efficiently separated out by roasting, crashing, acid leaching, neutralizing and precipitating Bi, replacing and precipitating Cu and precipitating Zn; and the yields of Sn, Bi, Cu and Zn are as high as 99.2%, 97.8%, 95.4% and 93.2%, respectively, and the product quality is good.
Description
Technical field
The present invention relates to the technology of from tin bismuth waste material, separating tin, bismuth, copper and zinc, belong to wet method and from solid waste, isolate non-ferrous metal element field.
Background technology
Among the present invention, reclaim the solid waste that is produced by the sn-bi alloy electroplating effluent and be called tin bismuth waste material, typical composition is: H
2O:37.72%, Bi:14.7%, Cu:1.56%, Sn:38.29%, Zn:1.35%, O:6.38%.
Because Bi, Sn metalline contained in the tin bismuth waste material are close, belong to amphoteric element, institute's Sn-Bi that forms or its oxide compound are difficult to carry out the common process separation.If before separation of Bismuth, copper, zinc, slough tin, be easy to follow-up metal recovery is become on treatment technology.But, about in the tin bismuth waste material to the feed separation of stanniferous, bismuth, copper and zinc, up to now, find to have similar bibliographical information as yet.
Prior art related to the present invention has: state's invention patent publication No. CN 1015143961 in 26 days Augusts in 2009; Disclosed " method of from the stanniferous lead anode slurry, separating tin, antimony " this method is earlier material to be added sodium-chlor with hydrochloric acid to carry out oxidation acid leaching; Make most tin, antimony, bismuth, copper etc. get into pickling liquor; Separate with lead, silver etc.; With ammonium chloride the form of the tin in the pickling liquor with ammonium stannic chloride optionally is precipitated out then, thereby realizes separating of tin and antimony, bismuth, copper.
Summary of the invention
Technical problem to be solved by this invention is: a kind of technology of from tin bismuth waste material, separating tin, bismuth, copper and zinc is provided; It creatively designs roasting and two-stage acid leaching step; Allow tin bismuth waste material before separation of Bismuth, copper, zinc, slough tin, follow-up metal recovery is become on treatment technology be easy to.
The technical scheme that the present invention adopts is such: a kind of technology of from tin bismuth waste material, separating tin, bismuth, copper and zinc, and processing step is following:
1. roasting
With tin bismuth waste material in 550～600 ℃ of following roastings; Make Sn wherein
+ 2Become Sn
+ 4, while SnO
2To become the α form that is insoluble to acid, alkali; Chemical equation: 2SnO+O
2=2 SnO
2
2. pulverize
The material that roasting is good is crushed to particle fineness and reaches 200 orders;
3. two-stage acid leaching
In one section leaching vat, add the hydrochloric acid of 1～2mol or the bismuth copper zinc lixiviating solution that two sections are returned, drop into the tin bismuth waste material that 2. step crushes by the solid-to-liquid ratio of 1:5; Be heated with stirring to more than 90 ℃; More than the restir insulation 2h; Filter, get one section leach liquor and one section filter residue; One section filter residue is added in two sections leaching vat, and the solid-to-liquid ratio of pressing 1:3～4 adds the hydrochloric acid of 1～2mol, is heated with stirring to 90 ℃, more than the insulation 2h, filters, and gets two sections leach liquors and two sections filter residues; With two sections filter residues of salt acid elution of 1～2mol, washings and two sections leach liquors are merged into bismuth copper zinc lixiviating solution, return in one section leaching vat; Two sections filter residues after the washing are the tin concentrate;
4. heavy bismuth neutralizes
3. one section leach liquor of step is neutralized to pH=3 with strong aqua, stirs and be cooled to 80 ℃, insulation; Ageing 1h filters, and filter residue is with the dilute hydrochloric acid solution washing of pH=3; The filtrating and the washings that merge this step are heavy bismuth filtrating, and the filter residue after this step washing is chlorine oxygen bismuth;
5. replace copper
In the heavy bismuth filtrating of 4. step, add zinc powder by stoichiometry and stir, the Cu in the control solution crosses the filtered liquid and the filter residue that filter displacement copper less than 1 ㎎/l; This filter residue is copper sponge;
6. depositing zinc
In the filtered liquid of 5. step displacement copper, add soda ash to pH>7.5, ageing is filtered, filtrating open circuit or reclaim ammonium chloride and sodium-chlor, filter residue is zinc carbonate.
Above-mentioned stoichiometry is meant that being replaced as the needed zinc powder amount of copper sponge fully by the amount of cupric ion in the heavy bismuth filtrating of participating in replacement(metathesis)reaction is stoichiometry.
Use technique effect of the present invention to be, the typical case can be formed is H
2The tin bismuth waste material of O:37.72%, Bi:14.7%, Cu:1.56%, Sn:38.29, Zn:1.35%, O:6.38% is separated into typical composition: the tin concentrate of Sn:56.3%, Bi:0.45%, Cu:0.051%, Zn:0.015%; Typical composition: Sn:1.11%; Bi:76.15%; Cu:0.031%; The chlorine oxygen bismuth of Zn:0.011%; Typical composition: Cu:0.013%; Zn:50.3%; Sn:0.001%; The copper sponge of Bi:0.001%, and typical composition: Cu:0.013%, Zn:50.3%; Sn:0.001%, the zinc carbonate of Bi:0.001%.Technical process is short, and waste back-cycling leaches and utilizes, or reclaims ammonium chloride and sodium-chlor.Environmental pollution is little.And can realize that the metallic tin rate of recovery is 99.2%; The bismuth rate of recovery is 97.8%; Copper recovery is 95.4%; Zinc recovery is 93.2%, and the product process stabilizing, and quality is good.
Embodiment
With embodiment the present invention is done detailed explanation below.
Embodiment
Taking by weighing typical case's composition is: H
2The tin bismuth waste material 50g of O:37.72%, Bi:14.7%, Cu:1.56%, Sn:38.29, Zn:1.35%, O:6.38% puts into retort furnace, 550～600 ℃ of controlled temperature, roasting 2h; Cooling is crushed to all through 200 orders, with two sections leach liquor 150ml; At 90 ℃, agitation condition leaches 2h down, and is cold slightly; Filter; Filtrating is one section leach liquor, composition analysis: Cu:5.11g/l, Zn:5.02g/l; Sn:230.8 ㎎/l, Bi:59.35g/l.Filter residue is with hydrochloric acid 120ml secondary leaching 2h under 90 ℃ of agitation conditions of 1.5mol, and is cold slightly, filters; Filtrating is two sections leach liquors; Filter residue 30ml, the salt acid elution of 1.5mol, washing lotion and two sections leach liquors merge and are used for one section leaching; Filter residue is the tin concentrate; Dry weight 20.7g, result of laboratory test: Cu:0.051%, Zn:0.015%; Sn:57.2%, Bi:0.45%.Tin metal yield: 99.2%.One section leach liquor is with 25% strong aqua 22.8g neutralization, and terminal point pH is 3, stirs; Be incubated 80 ℃, ageing 1h filters; Dilute hydrochloric acid solution washing filter residue with 20ml, pH value=3; Merge washing water and filtrating, filter residue is chlorine oxygen bismuth, dry weight 9.44g; Analytical results: Sn:1.11%; Bi:76.15%, Cu:0.058%, Zn:0.041%.Bismuth metal yield 97.8%, the filtrating behind the heavy bismuth adds zinc powder 0.8g, stirs 1h, filters, with a spot of water washing filter residue; Merge washing water and filtrating, be used for heavy zinc, filter residue is copper sponge, dry weight 0.81g; Analytical results: Sn:0.001%, Bi:0.05%, Cu:92.3%, Zn:2.50%.The metallic copper rate of recovery: 95.4%.
In displacement copper filtered liquid, add soda ash 2.5g, be heated with stirring to 60 ℃, depositing zinc, endpoint pH>7.Be warming up to 90 ℃ of insulations, stir 1h Chen Hua, filter, the filter cake water washing is, dry weight 3.03g.Analytical results: Sn:0.001%, Bi:0.001%, Cu:0.013%, Zn:50.3%.The total yield of metallic zinc: 93.2%.
Claims (1)
1. technology of from tin bismuth waste material, separating tin, bismuth, copper and zinc, it is characterized in that: processing step is following:
1. roasting
With tin bismuth waste material in 550～600 ℃ of following roastings; Make Sn wherein
+ 2Become Sn
+ 4, while SnO
2To become the α form that is insoluble to acid, alkali; Chemical equation: 2SnO+O
2=2 SnO
2
2. pulverize
The material that roasting is good is crushed to particle fineness and reaches 200 orders;
3. two-stage acid leaching
In one section leaching vat, add the hydrochloric acid of 1～2mol or the bismuth copper zinc lixiviating solution that two sections are returned, drop into the tin bismuth waste material that 2. step crushes by the solid-to-liquid ratio of 1:5; Be heated with stirring to more than 90 ℃; More than the restir insulation 2h; Filter, get one section leach liquor and one section filter residue; One section filter residue is added in two sections leaching vat, and the solid-to-liquid ratio of pressing 1:3～4 adds the hydrochloric acid of 1～2mol, is heated with stirring to 90 ℃, more than the insulation 2h, filters, and gets two sections leach liquors and two sections filter residues; With two sections filter residues of salt acid elution of 1～2mol, washings and two sections leach liquors are merged into bismuth copper zinc lixiviating solution, return in one section leaching vat; Two sections filter residues after the washing are the tin concentrate;
4. heavy bismuth neutralizes
3. one section leach liquor of step is neutralized to pH=3 with strong aqua, stirs and be cooled to 80 ℃, insulation; Ageing 1h filters, and filter residue is with the dilute hydrochloric acid solution washing of pH=3; The filtrating and the washings that merge this step are heavy bismuth filtrating, and the filter residue after this step washing is chlorine oxygen bismuth;
5. replace copper
In the heavy bismuth filtrating of 4. step, add zinc powder by stoichiometry and stir, the Cu in the control solution crosses the filtered liquid and the filter residue that filter displacement copper less than 1 ㎎/l; This filter residue is copper sponge;
6. depositing zinc
In the filtered liquid of 5. step displacement copper, add soda ash to pH>7.5, ageing is filtered, filtrating open circuit or reclaim ammonium chloride and sodium-chlor, filter residue is zinc carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201110297150A CN102304621A (en) | 2011-09-30 | 2011-09-30 | Process for separating out Sn, Bi, Cu and Zn from Sn-Bi waste material |
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|---|---|---|---|
| CN201110297150A CN102304621A (en) | 2011-09-30 | 2011-09-30 | Process for separating out Sn, Bi, Cu and Zn from Sn-Bi waste material |
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| CN102304621A true CN102304621A (en) | 2012-01-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108018431A (en) * | 2017-12-15 | 2018-05-11 | 郴州市金贵银业股份有限公司 | The recovery method of valuable metal in a kind of silver-zine slag |
| CN108085499A (en) * | 2017-12-13 | 2018-05-29 | 长沙汇聚环境技术有限公司 | A kind of separation and recovery method of tin bismuth waste material |
| CN109678199A (en) * | 2019-01-03 | 2019-04-26 | 江西铜业技术研究院有限公司 | A kind of technique producing stannic oxide as raw material using silver separating residues |
| CN112575194A (en) * | 2020-11-25 | 2021-03-30 | 中南大学 | Additive for strengthening tin oxidation volatilization in waste soldering tin and application thereof |
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| 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 |
| CN101768668A (en) * | 2010-01-07 | 2010-07-07 | 株洲冶炼集团股份有限公司 | Method for comprehensive recovery of lead and tin from alkaline refining slag of lead |
-
2011
- 2011-09-30 CN CN201110297150A patent/CN102304621A/en active Pending
Patent Citations (2)
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| 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 |
| CN101768668A (en) * | 2010-01-07 | 2010-07-07 | 株洲冶炼集团股份有限公司 | Method for comprehensive recovery of lead and tin from alkaline refining slag of lead |
Non-Patent Citations (5)
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| 《有色冶炼》 20011230 许秀莲等 从锡电解阳极泥中综合回收Pb、Bi的研究 , 第06期 * |
| 《赣南师范学院学报》 20040630 杨衍超等 锡阳极泥中回收锡铋铜铅的工业试验 , 第03期 * |
| 刘杨等: "不同形态SnO2纳米晶的制备", 《高等学校化学学报》, vol. 21, no. 10, 30 October 2000 (2000-10-30) * |
| 杨衍超等: "锡阳极泥中回收锡铋铜铅的工业试验", 《赣南师范学院学报》, no. 03, 30 June 2004 (2004-06-30) * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108085499A (en) * | 2017-12-13 | 2018-05-29 | 长沙汇聚环境技术有限公司 | A kind of separation and recovery method of tin bismuth waste material |
| CN108018431A (en) * | 2017-12-15 | 2018-05-11 | 郴州市金贵银业股份有限公司 | The recovery method of valuable metal in a kind of silver-zine slag |
| CN109678199A (en) * | 2019-01-03 | 2019-04-26 | 江西铜业技术研究院有限公司 | A kind of technique producing stannic oxide as raw material using silver separating residues |
| CN112575194A (en) * | 2020-11-25 | 2021-03-30 | 中南大学 | Additive for strengthening tin oxidation volatilization in waste soldering tin and application thereof |
| CN112575194B (en) * | 2020-11-25 | 2021-12-17 | 中南大学 | Additive for strengthening tin oxidation volatilization in waste soldering tin and application thereof |
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Application publication date: 20120104 |