CN104212995B - Lead bismuth alloy high-temperature alkaline detinning method - Google Patents
Lead bismuth alloy high-temperature alkaline detinning method Download PDFInfo
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- CN104212995B CN104212995B CN201410501028.3A CN201410501028A CN104212995B CN 104212995 B CN104212995 B CN 104212995B CN 201410501028 A CN201410501028 A CN 201410501028A CN 104212995 B CN104212995 B CN 104212995B
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Abstract
The invention discloses lead bismuth alloy high-temperature alkaline detinning method, it comprises the following steps: (1), by stanniferous lead bismuth alloy copper removal；(2), in market pot through copper removal lead bismuth alloy add industry NaCl cover bath surface, be warming up to 750 DEG C;(3), stirring；(4), one section carry tin, in melt, add appropriate alkaline slag former NaOH according to the stanniferous amount in lead bismuth alloy, continue stirring, until bath surface forms graininess scruff, drag for scruff；(5), two sections carry tin, continue in melt, add industry NaCl, then in melt, add alkalescence slag former NaOH, repeat step (2) and (3).The invention has the beneficial effects as follows that adding refining agent in fusion process covers, lead, bismuth volatilization loss amount under the high temperature conditions can be substantially reduced.Scruff can reclaim metallic tin further, carries the casting positive plate of the lead bismuth alloy after tin, complies fully with the electrowinning process requirement to impurity content.
Description
Technical field
The present invention relates to smelting field of nonferrous metal, particularly relate to lead bismuth alloy high-temperature alkaline detinning method.
Background technology
Tradition carries process of tin: oxygen-enriched a kind of stanniferous lead bismuth alloy of reduction furnace melting output, after copper removal, electrolysis,
Tin therein is extracted during cathode lead basic refining.This alkalescence of section after electrolysis carries process of tin and has the disadvantage in that tin
Being easier to be dispersed in electrolytic process and can not be enriched with in the earth of positive pole, electrolyte, cathode lead, in cathode lead, the rate of recovery is low；Produce
The alkaline scruff gone out is stanniferous low (about 1-2%), sells valuation coefficient low.
Chinese invention patent publication number CN101386924A discloses a kind of containing Pb, Cu, Sb, Bi, Sn, Ag, Au material
Detinning method, adds metal oxide in melted alloy and removes tin agent, but either which kind of detinning method is all deposited at high temperature
The volatile defect of lead, bismuth, causes unnecessary loss.
Summary of the invention
The technical problem to be solved in the present invention is existing detinning method except tin is inefficient, and lead, bismuth are in the process of extraction
In have volatilization loss, a kind of lead bismuth alloy high-temperature alkaline detinning method is provided for this.
The technical scheme is that lead bismuth alloy high-temperature alkaline detinning method, it comprises the following steps: (1), by stanniferous
Lead bismuth alloy copper removal；(2), through the lead bismuth alloy addition industry NaCl covering bath surface of copper removal, intensification in market pot
To 750 DEG C；(3), stir, melt is stirred, it is ensured that the melt at whole market pot edge also can flow therewith, now melt
In red look, viscosity is relatively low, limpid such as water, and stirring is until the white cigarette volatilized is thin, and 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 stirring,
Until bath surface forms graininess scruff, drag for scruff；(5), two sections carry tin, continue in melt, add industry NaCl, limit
Stirring limit is warming up to 750-780 DEG C, then adds alkalescence slag former NaOH in melt, repeats step (2) and (3).
The weight ratio of industry NaCl, Sn and NaOH described in such scheme is industry NaCl:Sn:NaOH=1:1.5:0.5.
It is 4h that a section of step described in such scheme (4) carries the tin duration, and two sections of step (5) carry the tin duration
For 3h.
The invention has the beneficial effects as follows that adding refining agent industry NaCl in fusion process covers, and can substantially reduce
Lead, bismuth volatilization loss amount under the high temperature conditions.Scruff can reclaim metallic tin further, carries the casting sun of the lead bismuth alloy after tin
Pole plate, complies fully with the electrowinning process requirement to impurity content.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:(1), by stanniferous lead bismuth alloy copper removal；(2), through the lead bismuth alloy addition of copper removal in market pot
Industry NaCl covers bath surface, is warming up to 750 DEG C；(3), stir, melt is stirred, it is ensured that whole market pot edge
Melt also can flow therewith, and now melt is red look, and viscosity is relatively low, limpid such as water, stirring until the white cigarette volatilized is thin,
Melt there will be the floating layer of layer；(4), one section carry tin, add in melt in right amount according to the stanniferous amount in lead bismuth alloy
Alkaline slag former NaOH, continue stirring, until bath surface formed graininess scruff, drag for scruff；(5), two sections carry tin, continue
Continue in melt, add industry NaCl, warming while stirring to 750 DEG C, then in melt, add alkalescence slag former NaOH, repeat
Step (2) and (3).
Embodiment 2:(1), by stanniferous lead bismuth alloy copper removal；(2), through the lead bismuth alloy addition of copper removal in market pot
Industry NaCl covers bath surface, is warming up to 750 DEG C；(3), stir, melt is stirred, it is ensured that whole market pot edge
Melt also can flow therewith, and now melt is red look, and viscosity is relatively low, limpid such as water, stirring until the white cigarette volatilized is thin,
Melt there will be the floating layer of layer；(4), one section carry tin, add in melt in right amount according to the stanniferous amount in lead bismuth alloy
Alkaline slag former NaOH, continue stirring, until bath surface formed graininess scruff, drag for scruff；(5), two sections carry tin, continue
Continue in melt, add industry NaCl, warming while stirring to 780 DEG C, then in melt, add alkalescence slag former NaOH, repeat
Step (2) and (3).
The chemical equation that period occurs is as follows: key reaction:
2Pb + O2 = 2PbO
PbO + Sn = SnO +Pb
3PbO + 2As = As2O3 +3Pb
3PbO + 2Sb = Sb2O3 +3Pb
It is likely to occur the most directly to react:
2As + 3O2= As2O3 ↑
Sn + O2= SnO2
2Sb + 3O2= Sb2O3 ↑
It is subsequently adding a kind of alkalescence slag former industrial caustic soda NaOH, reacts with oxide impurity, form solid-state scum silica frost, i.e. alkali
Property scruff, so drag for scruff, i.e. can reach removal of impurity purpose, scruff can as extract tin raw material continue with:
Slag making is reacted:
2NaOH + SnO2 =Na2SnO3 + H2O
Side reaction:
NaOH + PbO =NaPbO2 + H2O
Lead bismuth alloy is added in market pot, add heat fusing, use NaCl to cover at bath surface, the addition root of NaCl
Calculating according to stanniferous amount in lead bismuth alloy and determine, the fusing point of NaCl is 801 DEG C, so can reduce lead, bismuth evaporation, and play certain
Insulation effect, owing to Sb is just being prone to oxidation higher than its fusing point (630 DEG C), therefore, considers reaction speed, Elevated Temperature Conditions
After factor, by test, melt is warming up to about 750-780 DEG C optimum, uses thermocouple monitoring melt in temperature-rise period
Temperature.Intensification operation can use coal dust and iron powder to heat, and so can shorten the heating-up time, coal dust and the weight of iron powder
More obvious than for shortening the effect of heating-up time during 2:1, it is specifically shown in following table；
| Condition | Heating-up time |
| It is not added with iron powder and coal dust | 2h |
| Adding iron powder and coal dust, its weight ratio is 1:1 | 1.5h |
| Adding iron powder and coal dust, its weight ratio is 1:2 | 1.2h |
| Adding iron powder and coal dust, its weight ratio is 1:3 | 1.6h |
| Adding iron powder and coal dust, its weight ratio is 2:1 | 1.4h |
Preference of the present invention be on the basis of embodiment 1 or 2 by industry NaCl, Sn and NaOH weight ratio for industry
NaCl:Sn:NaOH=1:1.5:0.5, reacts the most complete under this ratio, and except tin effect is best, experimental data see table:
| 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 carries the tin duration is 4h, and two sections of step (5) carry the tin duration and are
3h, the time is the most long, reacts the most abundant, but the most unsustainable overlong time, prevent alloy high-temp sex change.
Concrete, residual lead bismuth alloy 20t after 25t market pot single treatment copper removal, stanniferous in alloy is 2.0% calculating: one
Duan Tixi processing industry NaCl about 110kg, add NaOH 50-55kg, stirring formed graininess alkalescence scruff, drag for scruff after, should
One section continues 4h except tin；Carrying out two sections and remove tin, two sections carry tin and add NaCl 70kg, add NaOH 35kg, repeat above operation and hold
Continuous 3h.The scruff of output is about 780kg, stanniferous can reach 55%, and Pb is about 10%.
If certain batch of lead bismuth alloy stanniferous up to 2.42%, higher than normal average value 2.0% by 0.42%, when first paragraph carries tin, essence
Refining agent industry NaCl, alkalescence slag former NaOH addition are identical, then can add about 110 refining agents, 55kg alkali when carrying tin for two sections
Property slag former, carry tin mixing time extend about 1 hour, subsequent technique needs can be met.
The advantages such as this method has simple to operate, and running cost is low, carry the lead bismuth alloy after tin stanniferous less than 0.1%, and
And during carrying tin, As, Sb are mainly oxidized to As2O3、Sb2O3Entering ring collection flue dust, a small amount of Sb enters scruff, and scruff can
To reclaim metallic tin further.Therefore, carry the casting positive plate of the lead bismuth alloy after tin, comply fully with electrowinning process to impurity content
Requirement.Compared with carrying tin with the electrolysis back segment of the lead of lead concentrate smelting flow process, advantage is to concentrate removal of impurities at leading portion, and can
Reclaim valuable metal therein, the electrolytic lead that then electrolysis output is qualified.With synthetic fibers are traditional except compared with process of tin, this work
The advantage of skill is that adding refining agent covers, and can substantially reduce lead, bismuth volatilization loss amount under the high temperature conditions.
Claims (2)
1. lead bismuth alloy high-temperature alkaline detinning method, is characterized in that it comprises the following steps: (1), removed by stanniferous lead bismuth alloy
Copper；(2), in market pot through copper removal lead bismuth alloy add industry NaCl cover bath surface, be warming up to 750 DEG C；(3),
Stirring, is stirred melt, it is ensured that the melt at whole market pot edge also can flow therewith, and now melt is red look, viscous
Spending relatively low, limpid such as water, stirring is until the white cigarette volatilized is thin, and melt there will be the floating layer of layer；(4), one section carries
Tin, adds appropriate alkaline slag former NaOH according to the stanniferous amount in lead bismuth alloy in melt, continues stirring, until melt table
Face forms graininess scruff, drags for scruff；(5), two sections carry tin, continue in melt, add industry NaCl, warming while stirring
To 750-780 DEG C, then in melt, add alkalescence slag former NaOH, repeat step (2) and (3), described industrial NaCl, Sn and
The weight ratio of NaOH is industry NaCl:Sn:NaOH=1:1.5:0.5.
2. lead bismuth alloy high-temperature alkaline detinning method as claimed in claim 1, is characterized in that one section of described step (4) carries tin
Duration is 4h, and it is 3h that two sections of step (5) carry the tin duration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410501028.3A CN104212995B (en) | 2014-09-26 | 2014-09-26 | Lead bismuth alloy high-temperature alkaline detinning method |
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| CN201410501028.3A CN104212995B (en) | 2014-09-26 | 2014-09-26 | Lead bismuth alloy high-temperature alkaline detinning method |
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| CN104212995A CN104212995A (en) | 2014-12-17 |
| CN104212995B true CN104212995B (en) | 2016-09-07 |
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| 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 |
| CN107475752B (en) * | 2017-08-31 | 2018-11-30 | 中南大学 | Clean metallurgy method and device for low-temperature molten salt electrolysis of tin dross |
| CN114293024B (en) * | 2021-12-30 | 2022-10-25 | 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 |
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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 |
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