CN102011015A - Method for removing arsenic, antimony and copper by refining raw lead - Google Patents
Method for removing arsenic, antimony and copper by refining raw lead Download PDFInfo
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- CN102011015A CN102011015A CN2010105988832A CN201010598883A CN102011015A CN 102011015 A CN102011015 A CN 102011015A CN 2010105988832 A CN2010105988832 A CN 2010105988832A CN 201010598883 A CN201010598883 A CN 201010598883A CN 102011015 A CN102011015 A CN 102011015A
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- lead
- copper
- antimony
- arsenic
- bullion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for removing arsenic, antimony and copper by refining raw lead. The invention aims to provide the method for removing the arsenic, antimony and copper by refining the raw lead. The method is characterized by comprising the following steps of: A, putting raw lead ingots into an open lead melting pot, and heating the raw lead ingots to the temperature of between 450 and 850 DEG C for melting lead into lead liquid; B, putting aluminum or aluminum alloy into the lead liquid obtained in the step A, fully mixing the aluminum or the aluminum alloy and the lead liquid with stirring, and generating scum which floats to the surface of the lead liquid; C, fishing the scum, namely fishing the scum generated in the step B after stirring to obtain the lead liquid removed with arsenic, antimony and copper; and D, casting ingots, namely casting the ingots by using the impurity removed lead liquid obtained in the step C to obtain lead ingots removed with the arsenic, antimony and copper. The method is mainly used for removing the arsenic, antimony and copper by refining the raw lead.
Description
Technical field
The present invention relates to a kind of production method of lead, particularly a kind of refining of lead bullion removes the method for arsenic, antimony, copper.
Background technology
Arsenic antimony is associated metal common in the lead ore concentrate, and general Sb content is 0.4～0.6%, and As is 0.5～0.6%, and in plumbous smelting process, behind lead ore concentrate process batching sintering, the retailoring of blast furnace, wherein 68% antimony enters lead bullion.Antimony in the lead bullion mainly plays the structure of improving the anode sludge when plumbous electrolysis, the anode sludge does not come off on the fixed anode, thereby plays skeleton function.The lead bullion anode contains antimony certain requirement, contains Sb＜0.3% o'clock, and anode sludge adhesion strength is low, is easy to fragmentary coming off and enters in the lead electrolytic solution; Contain Sb＞1% o'clock, can make lead electrolytic solution contain plumbum ion concentration and descend, the anode sludge thickens firmly, causes anode passivation, and when scrubbing lead anode, anode sludge difficult drop-off causes and scrubs the positive plate difficulty, thereby influences plumbous electrolytic ordinary production.It is 0.4～0.8% that plumbous smeltery contains Sb amount general requirement to the lead bullion anode.
Enter the continuous increase of the arsenic antimony copper content of lead system in recent years along with leady raw materials, arsenic antimony copper content is more and more higher in the lead bullion, Sb:0.9～1.5% in the general lead bullion, As:0.4～0.8%, Cu:＞0.1%, make plumbous electrolysis production have many problems, lead anode slurry thickens and does not come off firmly, scrub anode and need shovel the anode sludge, in this case, must carry out the refining of lead bullion and remove arsenic antimony copper with spades.
In addition, along with the recycling of secondary lead increases year by year, the Production of Secondary Lead cost is than primary lead low 38%, the secondary lead energy consumption only is 25.1～31.4% of a primary lead, one ton of secondary lead of every production can be saved 1360 kilograms of mark coals, reduces discharging useless 98.7 tons admittedly, economize on water 2.08 tons, reduce discharging 0.66 ton of sulfurous gas.China Production of Secondary Lead enterprise reaches hundreds of families, and secondary lead output accounted for 26% of plumbous production in 2008, was about about 850,000 tons.Generally all contain arsenic antimony copper in the raw materials for production of secondary lead, in the smelting process of secondary lead, most of arsenic antimony copper enters in the lead bullion, must remove arsenic antimony copper from lead bullion in subsequent handling, to satisfy the standard-required of lead bullion.
Traditional method that removes arsenic antimony from lead bullion has two kinds of oxidation refining and basic refinings.Oxidation refining be according to oxygen to the avidity of arsenic antimony greater than avidity to lead, and make arsenic antimony preferential oxidation become As
2O
3, Sb
2O
3, and be combined into 3PbOAs with PbO
2O
3And PbOSb
2O
3The formation scum silica frost is removed.Basic refining is with alkali metal compound (NaNO
3, NaOH and NaCl) mixture as the oxygenant of arsenic antimony, the oxidation of arsenic antimony generates Na
3AsO
4, Na
3SbO
4Slag making, thus remove arsenic antimony.Traditional method that removes Cu from lead bullion has the sulphur of adding copper removal and liquate copper removal.Add the sulphur copper removal be based on sulphur to the avidity of copper greater than avidity to lead, add and form the CuS compound behind the sulphur and become scum silica frost and remove copper; When the liquate copper removal was based on low temperature (326 ℃), the solubleness of copper was 0.06% in the plumbous liquid, and during the high plumbous liquid cooling of copper content, and copper is the Solid solution state and separates out and remove copper.But the oxidation refining temperature is generally 800 ℃～900 ℃, and plumbous volatilization is serious.Basic refining need add a large amount of NaOH, NaNO
3, in operating process, form alkali mist and NO
XGas can produce SO when adding the sulphur copper removal
2Gas.Problems such as all there is arsenic removal antimony copper weak effect in these methods, and the operating time is long, and environmental pollution is serious.
Summary of the invention
The object of the present invention is to provide a kind of refining of lead bullion to remove the method for arsenic, antimony, copper, it adopts the method that adds Al or Al alloy block (grain or powder) in the fused molten bullion, makes arsenic, antimony, copper in Al and the lead bullion form AsAl, SbAl and CuAl
2Form scum silica frost and remove arsenic, antimony, copper Deng compound come-up to plumbous bath surface, and Al is insoluble among the Pb, output satisfies the lead pig of next procedure requirement.
Technical solution of the present invention is: a kind of refining of lead bullion removes the method for arsenic, antimony, copper, it is characterized in that following steps:
A, base bullion lead is packed in the open market pot, heat fused is warmed up to 450-850 ℃, makes lead be fused into plumbous liquid;
B, aluminum or aluminum alloy is put in the plumbous liquid that steps A obtains, stirred, make aluminum or aluminum alloy and plumbous liquid thorough mixing and produce extremely plumbous liquid surface of scum silica frost come-up;
C, drag for slag, the scum silica frost of step B output is dragged for behind restir to the greatest extent, obtain the plumbous liquid of arsenic removal, antimony, copper;
D, ingot casting with the plumbous liquid ingot casting of removal of impurities that step C obtains, obtain the lead pig of arsenic removal, antimony, copper.
Described type of heating is electrically heated or combustion gas heating or solid fuel heating or electrical induction heating.
Described uncovered market pot is the molten bath of irony pot or clay plumbago crucible or burner hearth.
The temperature range that described base bullion lead heats up is 450 ℃～850 ℃.
Described churning time is 10～100min.
The invention has the beneficial effects as follows: utilize Al or Al alloy block (grain or powder) to form AsAl, SbAl and CuAl with arsenic, antimony, copper
2Form scum silica frost and the principle that is removed Deng compound come-up to plumbous bath surface, drawbacks such as compared with prior art, the present invention has overcome traditional oxidation refining that removes arsenic, antimony, copper from lead bullion and basic refining method arsenic removal antimony copper weak effect, the operating time is long, environmental pollution is serious; It is good that selected arsenic removal, antimony, the Tong Shiji of the present invention has a removal effect, and advantage such as arsenic removal, antimony, copper are fast has reduced plumbous volatilization, has eliminated alkali mist, NO
XAnd SO
2Gas, thus operating environment improved, be of value to production operation personnel physical and mental health, thereby environmental benefit is remarkable.Adopt method of the present invention refining from lead bullion to remove arsenic, antimony, copper, it is simple to have a technological operation, removal efficiency height, advantage such as production cost is low, and the operating time is short.
Embodiment
Below by embodiment the present invention and embodiment thereof are described in further detail.
A kind of refining of lead bullion removes the method for arsenic, antimony, copper, it is characterized in that following steps:
A, base bullion lead is packed in the open market pot, heat fused is warmed up to 450-850 ℃ and is, makes lead be fused into plumbous liquid;
B, aluminum or aluminum alloy is put in the plumbous liquid that steps A obtains, stirred, make aluminum or aluminum alloy and plumbous liquid thorough mixing and form AsAl, SbAl and CuAl
2The compound come-up is the scum silica frost shape to plumbous liquid surface;
C, drag for slag, the scum silica frost of step B output is dragged for behind restir to the greatest extent, obtain the plumbous liquid of arsenic removal, antimony, copper;
D, ingot casting with the plumbous liquid ingot casting of removal of impurities that step C obtains, obtain the lead pig of arsenic removal, antimony, copper.
Described type of heating is electrically heated or combustion gas heating or solid fuel heating or electrical induction heating.
Described uncovered market pot is the molten bath of irony pot or clay plumbago crucible or burner hearth.
The temperature range that described base bullion lead heats up is 450 ℃～850 ℃.
Described churning time is 10～100min.
Embodiment 1
With lead bullion electrically heated in the uncovered market pot of irony, after heat fused is warmed up to 450 ℃, in the fused molten bullion, add the Al piece more earlier in 1: 1 ratio, hand mixing 10min, the arsenic antimony copper in Al piece and the molten bullion forms AsAl, SbAl and CuAl
2Become scum silica frost Deng compound come-up to plumbous bath surface, stop to stir, drag for most plumbous dross on surface of fusant, ingot casting.Sample examination result: w
As: w 0.40%,
Sb: 0.80%.w
Cu：0.06％。
Embodiment 2
With lead bullion electrically heated in the uncovered market pot of irony, after heat fused is warmed up to 550 ℃, in the fused molten bullion, add the Al powder more earlier in 1: 2 ratio, mechanical stirring 25min, the arsenic antimony copper in Al powder and the molten bullion forms AsAl, SbAl and CuAl
2Become scum silica frost Deng compound come-up to plumbous bath surface, stop to stir, drag for most plumbous dross on surface of fusant, ingot casting.Sample examination result: w
As: w 0.38%,
Sb: 0.75%.w
Cu：0.05％。
Embodiment 3
With lead bullion electrically heated in the uncovered market pot of irony, after heat fused is warmed up to 650 ℃, in the fused molten bullion, add the Al powder more earlier in 1: 3 ratio, mechanical stirring 45min, the arsenic antimony copper in Al and the molten bullion forms AsAl, SbAl and CuAl
2Become scum silica frost Deng compound come-up to plumbous bath surface, stop to stir, drag for most plumbous dross on surface of fusant, ingot casting.Sample examination result: w
As: w 0.30%,
Sb: 0.70%.w
Cu：0.04％。
Embodiment 4
With lead bullion electrically heated in the uncovered market pot of irony, after heat fused is warmed up to 750 ℃, in the fused molten bullion, add the Al alloy block more earlier in 1: 4 ratio, mechanical stirring 85min, the arsenic antimony copper in Al and the molten bullion forms AsAl, SbAl and CuAl
2Become scum silica frost Deng compound come-up to plumbous bath surface, stop to stir, drag for most plumbous dross on surface of fusant, ingot casting.Sample examination result: w
As: w 0.24%,
Sb: 0.60%.w
Cu：0.04％。
Embodiment 5
With lead bullion electrically heated in the uncovered market pot of irony, after heat fused is warmed up to 850 ℃, in the fused molten bullion, add the Al alloy block more earlier in 1: 5 ratio, mechanical stirring 100min, the arsenic antimony copper in Al and the molten bullion forms AsAl, SbAl and CuAl
2Become scum silica frost Deng compound come-up to plumbous bath surface, stop to stir, drag for most plumbous dross on surface of fusant, ingot casting.Sample examination result: w
As: w 0.001%,
Sb: 0.003%.w
Cn：0.001％。
Claims (5)
1. the refining of lead bullion removes the method for arsenic, antimony, copper, it is characterized in that following steps:
A, base bullion lead is packed in the open market pot, heat fused is warmed up to 450-850 ℃, makes lead be fused into plumbous liquid;
B, aluminum or aluminum alloy is put in the plumbous liquid that steps A obtains, stirred, make aluminum or aluminum alloy and plumbous liquid thorough mixing and produce extremely plumbous liquid surface of scum silica frost come-up;
C, drag for slag, the scum silica frost of step B output is dragged for behind restir to the greatest extent, obtain the plumbous liquid of arsenic removal, antimony, copper;
D, ingot casting with the plumbous liquid ingot casting of removal of impurities that step C obtains, obtain the lead pig of arsenic removal, antimony, copper.
2. method according to claim 1, its feature is electrically heated or combustion gas heating or solid fuel heating or electrical induction heating at described type of heating.
3. method according to claim 1, its feature is in molten bath that described uncovered market pot is irony pot or clay plumbago crucible or burner hearth.
4. method according to claim 1, its feature is 450 ℃～850 ℃ in the temperature range that described base bullion lead heats up.
5. method according to claim 1, wherein said churning time are 10～100min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105988832A CN102011015A (en) | 2010-12-21 | 2010-12-21 | Method for removing arsenic, antimony and copper by refining raw lead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105988832A CN102011015A (en) | 2010-12-21 | 2010-12-21 | Method for removing arsenic, antimony and copper by refining raw lead |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102011015A true CN102011015A (en) | 2011-04-13 |
Family
ID=43841342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105988832A Pending CN102011015A (en) | 2010-12-21 | 2010-12-21 | Method for removing arsenic, antimony and copper by refining raw lead |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978416A (en) * | 2012-12-23 | 2013-03-20 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN103667737A (en) * | 2013-12-31 | 2014-03-26 | 湖南省桂阳银星有色冶炼有限公司 | Primary pyro-refining method for lead bullions |
| CN104561582A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Oxidation refining method of lead bullion |
| CN104561583A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Alkaline refining method of lead bullion |
| CN105603224A (en) * | 2015-12-25 | 2016-05-25 | 河南豫光金铅股份有限公司 | Smelting method for preparing lead-antimony alloy from lead-containing waste |
| CN106282574A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| CN106282659A (en) * | 2016-08-21 | 2017-01-04 | 株洲冶炼集团股份有限公司 | A kind of lead smelting removes antimony agent and except antimony technique with compound |
| CN107663592A (en) * | 2016-07-27 | 2018-02-06 | 江西金洋金属有限公司 | A kind of method that lead liquid is purified using deslagging agent |
| CN108893621A (en) * | 2018-06-15 | 2018-11-27 | 昆明理工大学 | A kind of method of pyro-refining lead bullion |
| CN110184475A (en) * | 2019-07-05 | 2019-08-30 | 云南驰宏资源综合利用有限公司 | A kind of method of high arsenic refining of lead bullion slag making enrichment arsenic |
| WO2019223559A1 (en) * | 2018-05-25 | 2019-11-28 | 江苏新春兴再生资源有限责任公司 | Selective antimony and arsenic removal and tin retaining agent for refining secondary crude lead, and use method |
| CN111826529A (en) * | 2020-06-28 | 2020-10-27 | 河南豫光金铅股份有限公司 | Separation smelting method of high-arsenic high-lead copper alloy |
| CN112899494A (en) * | 2021-01-27 | 2021-06-04 | 河南豫光金铅股份有限公司 | Method for continuous refining and decoppering of lead bullion and producing high-grade matte |
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| JPS5798637A (en) * | 1980-12-08 | 1982-06-18 | Nippon Mining Co Ltd | Removing method for arsenic and/or copper in fused metal |
| US4911755A (en) * | 1989-08-28 | 1990-03-27 | Cominco Ltd. | Method for the refining of lead |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978416A (en) * | 2012-12-23 | 2013-03-20 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN102978416B (en) * | 2012-12-23 | 2015-01-07 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN103667737A (en) * | 2013-12-31 | 2014-03-26 | 湖南省桂阳银星有色冶炼有限公司 | Primary pyro-refining method for lead bullions |
| CN104561582A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Oxidation refining method of lead bullion |
| CN104561583A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Alkaline refining method of lead bullion |
| CN105603224A (en) * | 2015-12-25 | 2016-05-25 | 河南豫光金铅股份有限公司 | Smelting method for preparing lead-antimony alloy from lead-containing waste |
| CN107663592A (en) * | 2016-07-27 | 2018-02-06 | 江西金洋金属有限公司 | A kind of method that lead liquid is purified using deslagging agent |
| CN106282659A (en) * | 2016-08-21 | 2017-01-04 | 株洲冶炼集团股份有限公司 | A kind of lead smelting removes antimony agent and except antimony technique with compound |
| CN106282574A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| CN106282574B (en) * | 2016-08-25 | 2018-07-24 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| WO2019223559A1 (en) * | 2018-05-25 | 2019-11-28 | 江苏新春兴再生资源有限责任公司 | Selective antimony and arsenic removal and tin retaining agent for refining secondary crude lead, and use method |
| EP3805413A4 (en) * | 2018-05-25 | 2022-03-09 | Jiangsu New Chunxing Resource Recycling Co. Ltd | Selective antimony and arsenic removal and tin retaining agent for refining secondary crude lead, and use method |
| US11414724B2 (en) | 2018-05-25 | 2022-08-16 | Jiangsu New Chunxing Resource Recycling Co., Ltd. | Agent for selective antimony and arsenic removal and tin retaining for refining secondary crude lead, and use method thereof |
| CN108893621A (en) * | 2018-06-15 | 2018-11-27 | 昆明理工大学 | A kind of method of pyro-refining lead bullion |
| CN108893621B (en) * | 2018-06-15 | 2021-03-30 | 昆明理工大学 | Method for fire refining of lead bullion |
| CN110184475A (en) * | 2019-07-05 | 2019-08-30 | 云南驰宏资源综合利用有限公司 | A kind of method of high arsenic refining of lead bullion slag making enrichment arsenic |
| CN111826529A (en) * | 2020-06-28 | 2020-10-27 | 河南豫光金铅股份有限公司 | Separation smelting method of high-arsenic high-lead copper alloy |
| CN111826529B (en) * | 2020-06-28 | 2021-10-22 | 河南豫光金铅股份有限公司 | Separation smelting method of high-arsenic high-lead copper alloy |
| CN112899494A (en) * | 2021-01-27 | 2021-06-04 | 河南豫光金铅股份有限公司 | Method for continuous refining and decoppering of lead bullion and producing high-grade matte |
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Application publication date: 20110413 |