CN104212995A - Lead bismuth alloy high-temperature alkaline detinning method - Google Patents
Lead bismuth alloy high-temperature alkaline detinning method Download PDFInfo
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- CN104212995A CN104212995A CN201410501028.3A CN201410501028A CN104212995A CN 104212995 A CN104212995 A CN 104212995A CN 201410501028 A CN201410501028 A CN 201410501028A CN 104212995 A CN104212995 A CN 104212995A
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Abstract
The invention discloses a lead bismuth alloy high-temperature alkaline detinning method, which comprises the following steps of: (1) removing copper from tin-containing lead bismuth alloy; (2) adding industrial NaCl into the lead bismuth alloy subjected to copper removal in a lead melting pot, covering the mixture on the surface of melt, and raising the temperature to 750 DEG C; (3) stirring the mixture; (4) carrying out primary tin extraction, adding a proper number of alkaline slag formers NaOH into the melt according to the tin content in the lead bismuth alloy, continuously stirring the mixture until particular tin slag is formed on the melt surface, and scooping out the tin slag; and (5) carrying out secondary tin extraction, continuously adding industrial NaCl into the melt, then, adding the alkaline slag formers NaOH into the melt, and repeating the step (2) and the step (3). The lead bismuth alloy high-temperature alkaline detinning method has the beneficial effects that refining agents are added in the melting process for coverage, so that the volatilization loss quantity of lead and bismuth under the high-temperature condition can be obviously reduced. The tin slag can be subjected to further metal tin recovery; the lead bismuth alloy after the tin extraction is used for anode plate casting; and the requirement of an electrolysis work procedure on the impurity content can be completely met.
Description
Technical field
The present invention relates to smelting field of nonferrous metal, relate in particular to lead bismuth alloy high-temperature alkaline detinning method.
Background technology
Tradition is carried process of tin: a kind of stanniferous lead bismuth alloy of oxygen enrichment reduction furnace melting output after copper removal, electrolysis, extracts tin wherein in the plumbous basic refining process of negative electrode.Thisly carry process of tin in electrolysis back segment alkalescence and have following shortcoming: tin is compared with being easily dispersed in the anode sludge, electrolytic solution, negative electrode lead and can not enrichment in electrolytic process, and the rate of recovery is low in negative electrode lead; The alkaline scruff stanniferous low (about 1-2%) of output, sells valuation coefficient low.
Chinese invention patent publication number CN101386924A discloses a kind of detinning method containing Pb, Cu, Sb, Bi, Sn, Ag, Au material, in the alloy of melting, add the agent of metal oxide detin, but no matter be which kind of detinning method is all deposited at high temperature plumbous, the volatile defect of bismuth, cause unnecessary loss.
Summary of the invention
The technical problem to be solved in the present invention is that existing detinning method detin efficiency is not high, and plumbous, bismuth has volatilization loss in leaching process, and a kind of lead bismuth alloy high-temperature alkaline detinning method is provided for this reason.
Technical scheme of the present invention is: lead bismuth alloy high-temperature alkaline detinning method, and it comprises the following steps: (1), by stanniferous lead bismuth alloy copper removal; (2), add industrial NaCl to cover bath surface to the lead bismuth alloy through copper removal in market pot, be warming up to 750 DEG C; (3), stir, melt is stirred, guarantee that the melt at whole market pot edge also can flow thereupon, now melt is red look, viscosity is lower, limpid as water, stirs until the white cigarette volatilizing is thin, melt there will be the floating layer of layer; (4), one section carry tin, in melt, add appropriate alkaline slag former NaOH according to the stanniferous amount in lead bismuth alloy, continue to stir, until bath surface forms particulate state scruff, drag for detin slag; (5), two sections carry tin, continue to add industrial NaCl in melt, warming while stirring is to 750-780 DEG C, then adds alkaline slag former NaOH, repeating step (2) and (3) in melt.
The weight ratio of industrial NaCl, Sn and NaOH described in such scheme is industrial NaCl:Sn:NaOH=1:1.5:0.5.
It is 4h that a section of step described in such scheme (4) is carried the tin time length, and it is 3h that two sections of step (5) are carried the tin time length.
The invention has the beneficial effects as follows and in fusion process, added refining agent industry NaCl to cover, can significantly reduce lead, the bismuth volatilization loss amount under hot conditions.Scruff can further reclaim metallic tin, carries the lead bismuth alloy casting positive plate after tin, meets the requirement of electrowinning process to foreign matter content completely.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:(1), by stanniferous lead bismuth alloy copper removal; (2), add industrial NaCl to cover bath surface to the lead bismuth alloy through copper removal in market pot, be warming up to 750 DEG C; (3), stir, melt is stirred, guarantee that the melt at whole market pot edge also can flow thereupon, now melt is red look, viscosity is lower, limpid as water, stirs until the white cigarette volatilizing is thin, melt there will be the floating layer of layer; (4), one section carry tin, in melt, add appropriate alkaline slag former NaOH according to the stanniferous amount in lead bismuth alloy, continue to stir, until bath surface forms particulate state scruff, drag for detin slag; (5), two sections carry tin, continue in melt, to add industrial NaCl, warming while stirring to 750 DEG C, then add alkaline slag former NaOH, repeating step (2) and (3) in melt.
Embodiment 2:(1), by stanniferous lead bismuth alloy copper removal; (2), add industrial NaCl to cover bath surface to the lead bismuth alloy through copper removal in market pot, be warming up to 750 DEG C; (3), stir, melt is stirred, guarantee that the melt at whole market pot edge also can flow thereupon, now melt is red look, viscosity is lower, limpid as water, stirs until the white cigarette volatilizing is thin, melt there will be the floating layer of layer; (4), one section carry tin, in melt, add appropriate alkaline slag former NaOH according to the stanniferous amount in lead bismuth alloy, continue to stir, until bath surface forms particulate state scruff, drag for detin slag; (5), two sections carry tin, continue in melt, to add industrial NaCl, warming while stirring to 780 DEG C, then add alkaline slag former NaOH, repeating step (2) and (3) in melt.
The chemical equation occurring is during this time as follows: principal reaction:
2Pb + O
2 = 2PbO
PbO + Sn = SnO +Pb
3PbO + 2As = As
2O
3 +3Pb
3PbO + 2Sb = Sb
2O
3 +3Pb
Also may there is a small amount of direct reaction:
2As + 3O
2 = As
2O
3 ↑
Sn + O
2 = SnO
2
2Sb + 3O
2 = Sb
2O
3 ↑
Then add a kind of alkaline slag former industrial caustic soda NaOH, react with oxide impurity, form solid-state scum silica frost, i.e. alkaline scruff, drags for detin slag like this, can reach removal of impurity object, and scruff can be used as the starting material continuation utilization of extracting tin:
Slag making reaction:
2NaOH + SnO
2 = Na
2SnO
3 + H
2O
Side reaction:
NaOH + PbO = NaPbO
2 + H
2O
Lead bismuth alloy is added in market pot, heat fused, adopt NaCl to cover bath surface, the add-on of NaCl is according to stanniferous amount calculative determination in lead bismuth alloy, the fusing point of NaCl is 801 DEG C, can reduce like this lead, bismuth evaporation, and play certain insulation effect, because Sb is just being easy to oxidation higher than its fusing point (630 DEG C), therefore, consider after the factor such as speed of response, Elevated Temperature Conditions, by test, melt is warming up to 750-780 DEG C of left and right optimum, adopts thermocouple monitoring melt temperature in temperature-rise period.Intensification operation can adopt coal dust and iron powder to heat, and can shorten the heating-up time like this, and the weight ratio of coal dust and iron powder shortens the effect of heating-up time while being 2:1 the most obvious, specifically sees the following form;
| Condition | Heating-up time |
| Do not add iron powder and coal dust | 2h |
| Add iron powder and coal dust, its weight ratio is 1:1 | 1.5h |
| Add iron powder and coal dust, its weight ratio is 1:2 | 1.2h |
| Add iron powder and coal dust, its weight ratio is 1:3 | 1.6h |
| Add iron powder and coal dust, its weight ratio is 2:1 | 1.4h |
Preference of the present invention is to be industrial NaCl:Sn:NaOH=1:1.5:0.5 by the weight ratio of industrial NaCl, Sn and NaOH on the basis of embodiment 1 or 2, reacts the most complete under this ratio, and detin effect is best, and experimental data sees the following form:
| NaCl:Sn:NaOH adding proportion | The stanniferous rate of lead bismuth alloy |
| 1:1.5:0.5 | 0.04% |
| 1:1.7:0.5 | 0.06% |
| 1:1.6:0.5 | 0.05% |
| 1:1.4:0.5 | 0.05% |
On the basis of above-described embodiment, one section is carried the tin time length is 4h, and it is 3h that two sections of step (5) are carried the tin time length, and the time is more of a specified duration, reacts more abundant, but also unsustainable overlong time prevents alloy high-temp sex change.
Concrete, residual lead bismuth alloy 20t after 25t market pot primary treatment copper removal, stanniferous in alloy is 2.0% calculating: carry the about 110kg of tin processing industry NaCl, add NaOH 50-55kg for one section, stir and form particulate state alkalescence scruff, drag for after detin slag, this section of detin continues 4h; Carry out two sections of detins, carry tin for two sections and add NaCl 70kg, add NaOH 35kg, repeat above operation and continue 3h.The scruff of output is about 780kg, and stanniferous 55%, the Pb that can reach is about 10%.
If certain batch of lead bismuth alloy is stanniferous up to 2.42%, higher by 0.42% than normal mean value 2.0%, when first paragraph is carried tin, refining agent industry NaCl, alkaline slag former NaOH add-on are identical, in the time carrying tin for two sections, can add approximately 110 refining agents, 55kg alkalescence slag former, the churning time of carrying tin extends approximately 1 hour, can meet subsequent technique needs.
The advantages such as present method has simple to operate, and running cost is low, carrying that lead bismuth alloy after tin is stanniferous can be lower than 0.1%, and carrying in tin process, As, Sb are mainly oxidized to As
2o
3, Sb
2o
3enter ring collection flue dust, a small amount of Sb enters scruff, and scruff can further reclaim metallic tin.Therefore, carry the lead bismuth alloy casting positive plate after tin, meet the requirement of electrowinning process to foreign matter content completely.The electrolysis back segment of smelting flow process with the lead of lead ore concentrate is carried compared with tin, and advantage is to concentrate removal of impurities at leading portion, and recyclable valuable metal wherein, the electrolytic lead that then electrolysis output is qualified.Traditional with synthon removes compared with process of tin, and the advantage of this technique is to have added refining agent to cover, and can significantly reduce lead, the bismuth volatilization loss amount under hot conditions.
Claims (3)
1. lead bismuth alloy high-temperature alkaline detinning method, is characterized in that it comprises the following steps: (1), by stanniferous lead bismuth alloy copper removal; (2), add industrial NaCl to cover bath surface to the lead bismuth alloy through copper removal in market pot, be warming up to 750 DEG C; (3), stir, melt is stirred, guarantee that the melt at whole market pot edge also can flow thereupon, now melt is red look, viscosity is lower, limpid as water, stirs until the white cigarette volatilizing is thin, melt there will be the floating layer of layer; (4), one section carry tin, in melt, add appropriate alkaline slag former NaOH according to the stanniferous amount in lead bismuth alloy, continue to stir, until bath surface forms particulate state scruff, drag for detin slag; (5), two sections carry tin, continue to add industrial NaCl in melt, warming while stirring is to 750-780 DEG C, then adds alkaline slag former NaOH, repeating step (2) and (3) in melt.
2. lead bismuth alloy high-temperature alkaline detinning method as claimed in claim 1, the weight ratio that it is characterized in that described industrial NaCl, Sn and NaOH is industrial NaCl:Sn:NaOH=1:1.5:0.5.
3. lead bismuth alloy high-temperature alkaline detinning method as claimed in claim 2, is characterized in that it is 4h that a section of described step (4) is carried the tin time length, and it is 3h that two sections of step (5) are carried the tin time length.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
| CN104212995A true CN104212995A (en) | 2014-12-17 |
| CN104212995B CN104212995B (en) | 2016-09-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106514123A (en) * | 2015-09-15 | 2017-03-22 | 常州兰翔机械有限责任公司 | Method for removing tin and bismuth fusible alloy residues on part surfaces |
| CN107475752A (en) * | 2017-08-31 | 2017-12-15 | 中南大学 | Clean metallurgy method and device for low-temperature molten salt electrolysis of tin dross |
| CN114293024A (en) * | 2021-12-30 | 2022-04-08 | 耒阳市焱鑫有色金属有限公司 | Refining method for recovering tin, tellurium and copper from crude lead |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB244424A (en) * | 1924-12-11 | 1927-01-17 | Henry Harris | Improvements relating to the treatment of impure molten metal and molten metallic masses |
| GB303328A (en) * | 1928-05-29 | 1929-01-03 | Henry Harris | Improvements in the purification of antimonial lead alloys and other antimonial metals |
| CN101705372A (en) * | 2009-11-25 | 2010-05-12 | 郴州市金贵银业股份有限公司 | Process for extracting tin from wet lead with high tin content |
-
2014
- 2014-09-26 CN CN201410501028.3A patent/CN104212995B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB244424A (en) * | 1924-12-11 | 1927-01-17 | Henry Harris | Improvements relating to the treatment of impure molten metal and molten metallic masses |
| GB303328A (en) * | 1928-05-29 | 1929-01-03 | Henry Harris | Improvements in the purification of antimonial lead alloys and other antimonial metals |
| CN101705372A (en) * | 2009-11-25 | 2010-05-12 | 郴州市金贵银业股份有限公司 | Process for extracting tin from wet lead with high tin content |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106514123A (en) * | 2015-09-15 | 2017-03-22 | 常州兰翔机械有限责任公司 | Method for removing tin and bismuth fusible alloy residues on part surfaces |
| CN106514123B (en) * | 2015-09-15 | 2018-06-26 | 中国航发常州兰翔机械有限责任公司 | A kind of piece surface tin bismuth fusible alloy residue minimizing technology |
| CN107475752A (en) * | 2017-08-31 | 2017-12-15 | 中南大学 | Clean metallurgy method and device for low-temperature molten salt electrolysis of tin dross |
| CN114293024A (en) * | 2021-12-30 | 2022-04-08 | 耒阳市焱鑫有色金属有限公司 | Refining method for recovering tin, tellurium and copper from crude lead |
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| Publication number | Publication date |
|---|---|
| CN104212995B (en) | 2016-09-07 |
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