CN103924094A - Method for treating copper dross - Google Patents

Method for treating copper dross Download PDF

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Publication number
CN103924094A
CN103924094A CN201410153331.9A CN201410153331A CN103924094A CN 103924094 A CN103924094 A CN 103924094A CN 201410153331 A CN201410153331 A CN 201410153331A CN 103924094 A CN103924094 A CN 103924094A
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copper
slag
smelting
copper dross
lead
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CN201410153331.9A
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CN103924094B (en
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李小兵
张立
李伟伟
卢珺珺
卢国才
房红俊
卢海军
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JIYUAN WANYANG SMELTING (GROUP) CO Ltd
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JIYUAN WANYANG SMELTING (GROUP) CO Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention provides a method for treating copper dross. According to the method, copper dross is treated by using an oxygen enrichment molten pool smelting side blowing furnace, coal granules are adopted as a reducing agent and fuel, copper dross, pure alkali, pyrite and water granulated slag are adopted for blending, together with the coal granules, are fed into the furnace from the feeding hole of the oxygen enrichment molten pool smelting side blowing furnace through a belt, and are blown into an oxygen enrichment air smelting pool for smelting so as to obtain crude lead, copper matte, furnace slag and high-temperature flue gas. By adopting the method provided by the invention, continuous feeding is achieved; due to adoption of a DCS automatic control technique, the working intensity of operators is low, the flushing and casting environment is good, the side blowing treatment bed is high in capacity, the efficiency of the smelting pool is high, the metal recycling rate is high, and the smelting energy consumption is low.

Description

A kind of method of processing copper dross slag
Technical field
The invention belongs to metallurgical technology field, relate to a kind of method of processing copper dross slag.
Background technology
In prior art, copper dross slag treatment process has reflection oven process, Blast Furnace Method, converter process, electric furnace process, pickling process, ammonia leaching process etc.
Wherein, reflection oven process technique labor condition is poor, thermo-efficiency is low and blowing-ouf of lines piece, maintenance are frequent, is classified as time limit by country and eliminates technique.Blast Furnace Method is processed copper dross slag, and plumbous of high grade in copper matte regulus, copper grade is low, Cu/Pb lower (only having 2~3), and the rate of recovery plumbous and copper is low, and a large amount of copper is stayed in lead bullion, and a large amount of lead enter copper matte regulus, cause copper, arsenic and precious metal to circulate during the course.Rotary kiln (claiming again rotary furnace) is processed copper dross slag and is had large (5~6%) of diesel consumption, the problem that production cost is higher.There is power consumption high (power consumption 340~380kwh/t, coke 40~50kg/t) in electric furnace process, the shortcomings such as running cost expense height are difficult in the area of power tense realize.Pickling process, ammonia leaching process, owing to being all to utilize metallic copper in copper dross slag and the reaction principle of solvent, are applicable to the high copper dross slag of Treatment of Copper, deal with uneconomically for the low copper dross slag of cupric, and wet processing cost is high.
The patent No. is that the patent of invention of ZL200810058951.9 discloses a kind of method of processing copper dross slag with converter, and the method comprises prepares burden copper dross slag, soda ash, iron filings or sulfurous iron ore and cigarette according to certain ratio, add retailoring in converter.Control 700~800 DEG C of temperature, smelt 1.5~2 hours, the metal form lead in copper dross slag is separated with copper, thereafter improve temperature to 1100~1250 DEG C of slag temperature of superheat, smelt 2.5~3 hours, make plumbous compound reduction generate metallic lead, copper enters matte and has realized asunder copper and lead.Scum silica frost on matte and lead bullion is pulled out, obtained matte and lead bullion.The method is made reductive agent, is blasted air and do fuel with diesel oil with coal.
Application number is the smelting process that 201010582745.5 patent of invention discloses a kind of copper dross slag, and the method comprises copper dross slag oxidation blowing output silver-bearing copper bismuth alloy, flue dust and chloride slag; Silver-bearing copper bismuth alloy electrolysis output cathode copper and copper anode mud, copper anode mud leaches, and leach liquor first heavy bismuth obtains chlorine oxygen bismuth, and chlorine oxygen bismuth is through the thick bismuth of retailoring output, more heavy copper obtains copper hydroxide, the thick silver of leached mud rotary kiln melting output, flue dust and oxidation sludge; Thick silver-colored electrolysis output finished product silver and silver anode slime reclaim Au, Pt, Pd from silver anode slime; Oxidation sludge and oxidation sludge retailoring of blast furnace obtain lead antimony alloy, flue dust and slag, and lead antimony alloy reverberatory smelting obtains lead bullion and flue dust; Flue dust reverberatory smelting output lead bullion and weisspiessglanz, weisspiessglanz retailoring output needle antimony; Lead bullion and lead bullion electrolysis output lead and lead anode slurry, reclaim gold and silver from lead anode slurry.The technical process complexity that the method is taked, output intermediate material is many.
Application number is that 201110343390.9 patent of invention discloses and a kind ofly separates that refining is plumbous produces copper and silver-colored method in copper dross slag, the method comprises the plumbous refining copper dross slag solid materials that produces, be placed under vacuum condition, after repeatedly heating up, being incubated, collect volatile matter, condensation obtains pb-ag alloy, and remaining solid is to slough plumbous and silver-colored copper alloy; Enter conventional plumbous smelting procedure or electrorefining operation using pb-ag alloy as raw material, silver is enriched in the anode sludge, is recycled silver again; Slough plumbous and silver-colored copper alloy directly as raw material, be recycled metallic copper with conventional way.But the hollow furnace apparatus that the method adopts is difficult to maximize at present, cannot realize scale production.
Application number is that 201210160123.2 patent of invention discloses a kind of method that lead bullion is produced in copper dross slag side-blown melting, the method comprises prepares burden copper dross slag, soda ash, sulfurous iron ore according to the ratio of 100:8~10:6~8, uniform feeding 1~2 hour, 600~800 DEG C of feed temperatures evenly blast hard coal with high-pressure blast simultaneously; Finish material 600~800 DEG C of meltings after 1~2 hour, temperature is increased to 1100~1200 DEG C of meltings 2~3 hours again, the metallic lead in copper dross slag and chemical combination state lead are all entered lead bullion by melting; Stop anthracitic blasting, clarified separation, after 0.5~1 hour, is first emitted lead bullion and matte by siphon, then opens cinder notch and emit slag, and high-temperature flue gas is up to standard emptying through waste heat recovery, after gathering dust.The method adopts is interrupted mode of operation, blasts hard coal carry out melting reaction with high-pressure air, and production efficiency is low, and melting energy consumption is high, and processing charges is high.
Summary of the invention
Therefore, the object of the invention is for the deficiencies in the prior art, a kind of new copper dross slag treatment process is provided, and method provided by the invention can realize continuous charging, DCS automatic control technology, labor strength is low, flushing and casting environment is good, and it is large that side-blown converter is processed bed ability, and bath smelting efficiency is high, metal recovery rate is high, and smelting energy consumption is low.
The invention provides a kind of method of processing copper dross slag, described method adopts oxygen enriched molten bath side-blown converter for smelting to process copper dross slag, uses coal grain to do reductive agent and fuel.Prepare burden with copper dross slag, soda ash, sulfurous iron ore and grain slag, enter stove through belt from oxygen enriched molten bath side-blown converter for smelting feed opening together with coal grain, and blast oxygen-rich air bath smelting, obtain lead bullion, matte, slag and high-temperature flue gas.
Particularly, the method for processing copper dross slag provided by the invention comprises the following steps:
1) copper dross slag, soda ash, sulfurous iron ore and grain slag are prepared burden with the ratio of mass ratio 100:2~4:5~20:5~15,10~30t/h incessantly evenly feeds intake, coal 0.8~3t/h from oxygen enriched molten bath side-blown converter for smelting feed opening, blasts oxygen-rich air 2000~3000m simultaneously 3/ h, oxygen concn is 40~80%; Control melting atmosphere (reducing degree) and carry out retailoring;
3) metallic lead in copper dross slag and chemical combination state lead smelting enter lead bullion, discharge by siphon siphon, and copper is discharged by matte mouth with copper matte regulus form, and the slag that contains very low lead and copper is discharged by cinder notch, produces high-temperature flue gas simultaneously.
Preferably, the mass ratio of described copper dross slag, soda ash, sulfurous iron ore and grain slag is 100:2:8:8
Preferably, the specification of described oxygen enriched molten bath side-blown converter for smelting is 4-12m 2, be preferably selected from 4.8m 2, 6m 2, 7.2m 2, 8.4m 2, 12m 2oxygen enriched molten bath side-blown converter for smelting; Further preferably, the specification of oxygen enriched molten bath side-blown converter for smelting is 6m 2;
Preferably, described oxygen enriched molten bath side-blown converter for smelting bottom is provided with safe mouthful, while there is blowing out situation, discharges end lead by safety mouthful.
Preferably, described copper dross slag is the copper dross slag of leaded 40~80wt%, cupric 4~12wt%.
Preferably, described sulfurous iron ore sulphur content is 15~48wt%;
Preferably, process the high-temperature flue gas that produces in copper dross slag by waste heat boiler recovery waste heat, pulse dust collector gather dust, qualified discharge after thionizer desulfurization, described emission standard is SO 2concentration is less than 220mg/m 3.
Preferably, siphon is kept clear, freely discharge lead bullion according to the lead tolerance that enters stove batching.
Preferably, in step 3), be 1~4h the interval that described matte mouth is discharged the copper of copper matte regulus form;
Preferably, be 2~4h the interval of described cinder notch discharge slag.
Preferably, described coal grain consumption is 8~15% of copper dross slag quality, and further preferably, described coal grain consumption is 8~11% of copper dross slag quality; Again further preferably, described coal grain consumption is 9.3% of copper dross slag quality.
The present invention has advantages of compared with conventional art:
1) smelt low, the processing charges economy of energy consumption, detailed data is in table 1
The common copper dross slag of table 1 is processed energy consumption index
As can be seen from Table 1, energy consumption of the present invention is lower than the energy consumption of other several techniques.The present invention uses coal grain as fuel or reductive agent, and with coke, diesel oil or electric energy, hard coal is compared, and coal grain is cheap, and buying is convenient.The present invention adopts oxygen enriched molten bath melting, and exhaust gas volumn is few, and heat utilization efficiency is the highest, and other several techniques all blast air-melted, and exhaust gas volumn is large, and thermal losses is high.Therefore the present invention smelts that energy consumption is low, processing charges economy.
2) the present invention adopts the production of working continuously, and other several techniques all adopt interruption mode of operation, and therefore smelting efficiency of the present invention is high, is more suitable for technical scaleization application.
3) pickling process, ammonia leaching process are owing to being all the reaction process of metallic copper and solvent, and higher its direct yield of copper content is higher, are therefore applicable to the high copper dross slag of Treatment of Copper, deal with uneconomical for the low copper dross slag of cupric.
But the present invention is easy to, by the copper enrichment in copper dross slag low cupric, obtain Cu/Pb than the matte of high (4~10).
4) in patent of invention " a kind of method that lead bullion is produced in copper dross slag side-blown melting " the output slag that application number is 201210160123.2, valuable metal is high, and slag is containing Pb≤2.8%, and slag is containing Cu≤0.5%, and metal straight yield is low.Slag of the present invention is containing Pb≤1.5%, and slag is containing Cu≤0.3%, and metal straight yield and the rate of recovery are high.
Brief description of the drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 is the schema of one embodiment of the invention.
Fig. 2 is the schema of another embodiment of the invention.
Embodiment
embodiment 1
As shown in Figure 1, at 6m 2oxygen enriched molten bath side-blown converter for smelting in, by copper dross slag (Pb72%, Cu8.1%), soda ash, sulfurous iron ore (S32%), grain slag, prepare burden according to the ratio of mass ratio 100:3:6:12, the 3h that feeds intake, amounts to 60t, coal 6.6t from feed opening, blasts oxygen-rich air 2300Nm simultaneously 3/ h, oxygen concentration 51%.
Emit lead bullion by plumbous siphon, output lead bullion 33.6t(is leaded 97.5%, Cu0.4%), the lead bullion of output needs delead refining; By matte mouth output matte (leaded 5.4%, Cu43%) 8.4t, the matte of output removes converter smelting; Put slag (leaded 1.4%, Cu0.28%) 11.7t by slag notch, this slag is for selling outward; High-temperature flue gas is by waste heat boiler recovery waste heat, after pulsating collection, through thionizer desulfurization, qualified discharge (SO 2concentration is less than 220mg/m 3), the flue dust wherein obtaining in waste heat boiler and in pulsating collection carries out delead smelting.
Output cigarette ash 5.2t, coal grain consumption is 13.3% of copper dross slag amount, vertical yield 91.8%, the rate of recovery 99.5%, copper recovery 89.9%, matte Cu/Pb ratio is 7.96.
embodiment 2:
As shown in Figure 1, at 6m 2side-blown converter in, by copper dross slag (Pb72%, Cu8.1%), soda ash, sulfurous iron ore (S32%), grain slag, prepare burden according to the ratio of mass ratio 100:3:5:8, the 4h that feeds intake, amounts to 80t, coal 8.8t from feed opening, blasts oxygen-rich air 2500Nm simultaneously 3/ h, oxygen concentration 54%.
Emit lead bullion by plumbous siphon, output lead bullion 47.3t(is leaded 97.5%, Cu0.4%), cigarette ash 8.3t, slag (leaded 1.3%, Cu0.25%) 12.1t, matte (leaded 5.1%, Cu46%) 11.7t, vertical yield 92.9%, the rate of recovery 99.7%, copper recovery 92.2%, matte Cu/Pb ratio is 9.02.
embodiment 3:
As shown in Figure 1, at 6m 2side-blown converter in, by copper dross slag (Pb57%, Cu10.2%), soda ash, sulfurous iron ore (S32%), grain slag, prepare burden according to the ratio of mass ratio 100:2:8:8, the 4h that feeds intake, amounts to 48t, coal 3.8t from feed opening, blasts oxygen-rich air 2300Nm simultaneously 3/ h, oxygen concentration 56%.
Emit lead bullion by plumbous siphon, output lead bullion 21.6t(is leaded 97.5%, Cu0.4%), cigarette ash 4.9t, slag (leaded 1.2%, Cu0.24%) 13.5t, matte (leaded 5.2%, Cu48%) 7.7t, vertical yield 93.1%, the rate of recovery 99.3%, copper recovery 89.1%, matte Cu/Pb ratio is 9.1.
embodiment 4:
As shown in Figure 1, at 6m 2side-blown converter in, by copper dross slag (Pb57%, Cu10.2%), soda ash, sulfurous iron ore (S32%), grain slag, prepare burden according to the ratio of mass ratio 100:4:15:5, the 4h that feeds intake, amounts to 60t, coal 7.3t from feed opening, blasts oxygen-rich air 2300Nm simultaneously 3/ h, oxygen concentration 57%.
Emit lead bullion by plumbous siphon, output lead bullion 24.3t(is leaded 97.5%, Cu0.4%), cigarette ash 4.7t, slag (leaded 2.5%, Cu0.48%) 23.8t, matte (leaded 8.7%, Cu35%) 10.5t, vertical yield 85.9%, the rate of recovery 97.8%, copper recovery 74.5%, matte Cu/Pb ratio is 4.02.

Claims (10)

1. process the method for copper dross slag for one kind, described method adopts oxygen enriched molten bath side-blown converter for smelting to process copper dross slag, use coal grain to do reductive agent and fuel, prepare burden with copper dross slag, soda ash, sulfurous iron ore and grain slag, enter stove from oxygen enriched molten bath side-blown converter for smelting feed opening together with coal grain, and blast oxygen-rich air bath smelting, obtain lead bullion, matte, slag and high-temperature flue gas.
2. method according to claim 1, wherein, said method comprising the steps of:
1) copper dross slag, soda ash, sulfurous iron ore and grain slag are prepared burden with the ratio of mass ratio 100:2~4:5~20:5~15,10~30t/h incessantly evenly feeds intake, coal 0.8~3t/h from oxygen enriched molten bath side-blown converter for smelting feed opening, blasts oxygen-rich air 2000~3000m simultaneously 3/ h, oxygen concn is 40~80%; Carry out retailoring;
3) metallic lead in copper dross slag and chemical combination state lead smelting enter lead bullion, discharge by siphon siphon, and copper is discharged by matte mouth with copper matte regulus form, and the slag that contains very low lead and copper is discharged by cinder notch, produces high-temperature flue gas simultaneously.
3. method according to claim 2, wherein, the mass ratio of described copper dross slag, soda ash, sulfurous iron ore and grain slag is 100:2~4:5~20:5~15.
4. according to the method described in any one in claim 1-3, wherein, the specification of described oxygen enriched molten bath side-blown converter for smelting is 4-12m 2, be preferably selected from 4.8m 2, 6m 2, 7.2m 2, 8.4m 2, 12m 2oxygen enriched molten bath side-blown converter for smelting; Further preferably, the specification of oxygen enriched molten bath side-blown converter for smelting is 6m 2;
Preferably, described oxygen enriched molten bath side-blown converter for smelting bottom is provided with safe mouthful, while there is blowing out situation, discharges end lead by safety mouthful.
5. according to the method described in any one in claim 1-4, wherein, described copper dross slag is the copper dross slag of leaded 40~80wt%, cupric 4~12wt%.
6. according to the method described in any one in claim 1-5, wherein, described sulfurous iron ore sulphur content is 15~48wt%.
7. method according to claim 1, wherein, described high-temperature flue gas is by waste heat boiler recovery waste heat, and pulse dust collector gathers dust, qualified discharge after thionizer desulfurization, and described emission standard is SO 2concentration is less than 220mg/m 3.
8. method according to claim 1, be 1~4h the interval that wherein said matte mouth is discharged the copper of copper matte regulus form.
9. method according to claim 1, be 2~4h the interval that wherein said cinder notch is discharged slag.
10. method according to claim 1, wherein, described coal grain consumption is 8~15% of copper dross slag quality, further preferably, described coal grain consumption is 8~12% of copper dross slag quality; Again further preferably, described coal grain consumption is 9.3% of copper dross slag quality.
CN201410153331.9A 2014-04-16 2014-04-16 A kind of method processing copper scum silica frost Active CN103924094B (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232925A (en) * 2014-09-30 2014-12-24 济源市欣欣实业有限公司 Method for carrying out mixed melting on multisource complex low-grade copper ores to produce white matte
CN104831078A (en) * 2015-04-21 2015-08-12 云南驰宏锌锗股份有限公司 Method for processing zinc wet smelting slag by use of warm slag side blowing reducing furnace
CN105132708A (en) * 2015-10-12 2015-12-09 湖南金旺铋业股份有限公司 Process method for sufficiently recycling precious metal from copper dross and copper matte
CN105838894A (en) * 2016-05-13 2016-08-10 中国恩菲工程技术有限公司 Process for treating copper dross through oxygen enrichment top-blowing smelting-settling separation
CN106834738A (en) * 2017-03-15 2017-06-13 中南大学 A kind of compound additive and application that copper is reclaimed for copper smelting slag
CN107099669A (en) * 2017-04-21 2017-08-29 昆明冶金研究院 A kind of method containing high-efficiency cleaning arsenic removal in copper ashes
CN107760879A (en) * 2017-10-23 2018-03-06 金川集团股份有限公司 A kind of method of twin furnace linkage processing Complicated Copper bismuth material
CN109022809A (en) * 2018-07-27 2018-12-18 郴州雄风环保科技有限公司 A kind of organic acid sodium-iron chip filter reduction melting copper dross slag new process
CN109439924A (en) * 2018-12-05 2019-03-08 湖南锐异资环科技有限公司 A kind of processing method of secondary lead-containing material
CN109517999A (en) * 2018-12-05 2019-03-26 湖南锐异资环科技有限公司 A kind of side-blown method of smelting of secondary lead-containing material
CN111719045A (en) * 2019-03-21 2020-09-29 个旧市锦星锑业有限公司 Oxygen-enriched intensified smelting method for horizontal reduction furnace

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CN101358286A (en) * 2008-09-25 2009-02-04 昆明理工大学 Method for treating copper scum using converter
CN102643996A (en) * 2012-05-23 2012-08-22 云南驰宏锌锗股份有限公司 Method for producing lead bullion by means of copper dross side-blown smelting
CN103667712A (en) * 2013-12-12 2014-03-26 中南大学 Method for smelting lead-containing waste and copper-containing waste synchronously in molten pool

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Publication number Priority date Publication date Assignee Title
CN101358286A (en) * 2008-09-25 2009-02-04 昆明理工大学 Method for treating copper scum using converter
CN102643996A (en) * 2012-05-23 2012-08-22 云南驰宏锌锗股份有限公司 Method for producing lead bullion by means of copper dross side-blown smelting
CN103667712A (en) * 2013-12-12 2014-03-26 中南大学 Method for smelting lead-containing waste and copper-containing waste synchronously in molten pool

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232925B (en) * 2014-09-30 2016-03-09 济源市欣欣实业有限公司 The method of the complicated Treating Low-grade Copper Ores producing white matte by mixed smelting of multi-source
CN104232925A (en) * 2014-09-30 2014-12-24 济源市欣欣实业有限公司 Method for carrying out mixed melting on multisource complex low-grade copper ores to produce white matte
CN104831078A (en) * 2015-04-21 2015-08-12 云南驰宏锌锗股份有限公司 Method for processing zinc wet smelting slag by use of warm slag side blowing reducing furnace
CN104831078B (en) * 2015-04-21 2017-11-07 云南驰宏锌锗股份有限公司 A kind of method that use warm sludge side-blown reduction stove handles zinc hydrometallurgy slag
CN105132708A (en) * 2015-10-12 2015-12-09 湖南金旺铋业股份有限公司 Process method for sufficiently recycling precious metal from copper dross and copper matte
CN105838894A (en) * 2016-05-13 2016-08-10 中国恩菲工程技术有限公司 Process for treating copper dross through oxygen enrichment top-blowing smelting-settling separation
CN106834738A (en) * 2017-03-15 2017-06-13 中南大学 A kind of compound additive and application that copper is reclaimed for copper smelting slag
CN107099669A (en) * 2017-04-21 2017-08-29 昆明冶金研究院 A kind of method containing high-efficiency cleaning arsenic removal in copper ashes
CN107760879A (en) * 2017-10-23 2018-03-06 金川集团股份有限公司 A kind of method of twin furnace linkage processing Complicated Copper bismuth material
CN109022809A (en) * 2018-07-27 2018-12-18 郴州雄风环保科技有限公司 A kind of organic acid sodium-iron chip filter reduction melting copper dross slag new process
CN109022809B (en) * 2018-07-27 2020-05-22 郴州雄风环保科技有限公司 Process for reducing and smelting copper dross by using sodium organic acid-scrap iron method
CN109439924A (en) * 2018-12-05 2019-03-08 湖南锐异资环科技有限公司 A kind of processing method of secondary lead-containing material
CN109517999A (en) * 2018-12-05 2019-03-26 湖南锐异资环科技有限公司 A kind of side-blown method of smelting of secondary lead-containing material
CN111719045A (en) * 2019-03-21 2020-09-29 个旧市锦星锑业有限公司 Oxygen-enriched intensified smelting method for horizontal reduction furnace

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