CN103695650A - Method for smelting lead paste of waste lead storage battery - Google Patents
Method for smelting lead paste of waste lead storage battery Download PDFInfo
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- CN103695650A CN103695650A CN201310721550.8A CN201310721550A CN103695650A CN 103695650 A CN103695650 A CN 103695650A CN 201310721550 A CN201310721550 A CN 201310721550A CN 103695650 A CN103695650 A CN 103695650A
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- lead
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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
Abstract
The invention discloses a method for smelting lead paste of a waste lead storage battery. The method comprises the following steps: mixing the lead paste of the waste lead storage battery with a reducer-coke or powdered coal, copper residues, iron ores, quartz sand and limestone, wherein the additive amount of the coke or the powdered coal is 10%-25% by weight of the lead paste of the waste lead storage battery, the weight of the copper residues is 5-10 times that of sulfur in the lead paste of the waste lead storage battery, the added limestone, quartz sand and iron ores meet the smelting slag requirements that the weight ratio of FeO to SiO2 is 1.2 to 1.75 and the weight ratio of CaO to SiO2 is (0.4-0.9) to 1; adding a mixture into a cylinder or a disk granulator for granulating; conveying granulated materials into a smelting furnace; filling the smelting furnace with oxygen-rich air for reduction smelting. According to the method, a reducing atmosphere is controlled, so that copper-sulfur concentrates are obtained by reacting the copper residues with sulfur in the waste lead storage battery while crude copper is produced, and lead, copper and sulfur are directly recovered; the recovery rate of crude copper is more than 98% and the comprehensive recovery rate of copper and sulfur is more than 95%.
Description
Technical field
The present invention relates to pyrometallurgical processes in field of metallurgy, particularly a kind of waste lead accumulator is containing the smelting novel method of lead plaster mud.
Background technology
Waste lead accumulator is the main raw material of secondary lead.The waste lead accumulator reclaiming, after being crushed to certain particle size, adopting the sorting system produce vulcanite such as waterpower or medium, plastics, lead antimony alloy particle and contains lead plaster mud, wherein containing lead plaster mud, mainly contains PbSO
4, PbO
2, PbO and Pb etc., at present from having pyrogenic process and two kinds for the treatment of process of wet method containing reclaiming metallic lead lead plaster mud.
Pyrometallurgical smelting containing lead plaster mud is generally the method that adopts retailoring.The reductive agent that retailoring adopts is breeze, coal dust or iron filings, after the flux mixes such as lead plaster mud and these reductive agents and Wingdale, river sand, sodium carbonate, adds and in smelting furnace, carries out reduction reaction output lead bullion, flue dust and slag.The type of furnace that retailoring adopts has blast furnace, reverberatory furnace, electric furnace or short rotary kiln etc.Although this method has, metal recovery rate is high, facility investment is few, simple operation and other advantages, has the shortcoming that smelting furnace efficiency of utilization is low, production energy consumption is high, contains low-concentration sulfur dioxide in the flue gas of output simultaneously, easily causes environmental pollution.It is the new technology of developing in recent years containing lead plaster mud that oxygen enrichment refines plumbous method processing, containing lead plaster mud and concentrate of lead sulfide ore, after the mixes such as sludging flux, add and in smelting furnace, carry out oxidizing semlting, in fusion process, pass into high-concentration oxygen, under the oxidation and stirring action of oxygen, containing lead plaster mud and concentrate of lead sulfide ore, at high temperature there is violent cross reaction, obtain lead bullion, lead oxidation slag and leaded flue dust, the lead bullion of output is sent to electrolytic refining plant and produces lead bullion, lead oxidation slag carries out retailoring, the sulfur dioxide flue gas that ash-laden gas obtains high density after electric dust collection device trapping lead fume ash is sent to acid making system production sulfuric acid.Oxygen enrichment refines that plumbous treatment process has that throughput is large, lead and sulfur recovery rate is high, the flue gas SO of good operational environment and generation
2concentration is conducive to the advantages such as relieving haperacidity, but because fusion process need to maintain higher temperature of reaction, therefore can provide the concentrate of lead sulfide ore allocation ratio of heat higher, often need to additionally add certain breeze or coal dust as auxiliary fuel simultaneously.
Wet treatment method containing lead plaster mud is first to carrying out wet method conversion containing lead plaster mud, adopt the transforming agents such as sodium carbonate, volatile salt or bicarbonate of ammonia to be converted into lead carbonate containing lead sulfate in lead plaster mud, containing the plumbic oxide in lead plaster mud, select to be translated into yellow lead oxide under the condition of the reductive agents such as ammonium sulphite, the product obtaining carries out retailoring output lead bullion or adopts the method for silicofluoric acid dissolvings-galvanic deposit to reclaim lead.The method environmental friendliness, metal recovery rate is high, and having main shortcoming is that throughput is little and production cost is higher.
Summary of the invention
In order to overcome above-mentioned processing containing the deficiency of lead plaster mud, the waste lead accumulator that the invention provides that a kind of comprehensive recovery is high, environmental friendliness, cost is low is containing lead plaster mud melting method.
The present invention is that the technical scheme adopting that achieves the above object is: by waste lead accumulator containing lead plaster mud and reductive agent coke or fine coal, contain copper ashes, iron ore, quartz sand, Wingdale and prepare burden according to certain ratio after; join in cylinder or disk pelletizing machine and granulate; material after granulation joins in smelting furnace and passes into oxygen-rich air and carries out retailoring, directly output lead bullion, copper matte regulus, smelting slag and flue dust.
Technological process and technical parameter that the present invention is concrete are as follows:
1 batching
Waste lead accumulator is prepared burden containing lead plaster mud and coke or fine coal, cupric slag charge, iron ore, Wingdale, quartz sand, coke or fine coal add-on be waste lead accumulator contain lead plaster mud weight 10% ~ 25%; The add-on of cupric slag charge is 5 ~ 10 times that waste lead accumulator contains sulfur-bearing weight in lead plaster mud; The Wingdale adding, quartz sand and iron ore meet smelting slag type and require as FeO and SiO
2weight ratio is 1.2 ~ 1.75:1, CaO and SiO
2weight ratio is 0.4 ~ 0.9:1; In gained mixture, Pb content is 15% ~ 60%.
2 granulate
Mixture is added and in nodulizer, mixes and granulate, control amount of water, after mixing, obtaining granularity is 6 ~ 25mm, moisture 5% ~ 10% enter stove material.
3 meltings
To enter stove material joins and in smelting furnace, carries out retailoring, smelting temperature is controlled at 1100 ~ 1300 ℃, pass into volumetric concentration simultaneously and be 21% ~ 50% oxygen-rich air, the oxygen-rich air volume passing into is 0.6 ~ 1.2:1 with the envelope-bulk to weight ratio that enters the weight of stove material, volume unit is cubic meter, the weight unit that enters stove material for kilogram, after melting 30 ~ 90min, emit successively lead bullion, copper matte regulus and smelting slag.The flue dust producing in fusion process, after negative pressure is gathered dust and cooled, returns to pelletization.The main chemical reactions occurring in fusion process is:
PbO
2+C=Pb+CO
2 （1）
2PbO+C=2Pb+CO
2 （2）
PbSO
4+2C+2Cu=Pb+Cu
2S+2CO
2 （3）
PbSO
4+3C+2CuO=Pb+Cu
2S+3CO
2 （4）
FeO+SiO
2= FeO·SiO
2 （5）
CaO+SiO
2= CaO·SiO
2 （6）
Described coke or fine coal are for containing C > 70%.
The Wingdale adding is containing CaO > 45%, and quartz sand is containing SiO
2>90%, iron ore iron content > 35%.
Described cupric slag charge is bessemerized slag or copper refining slag for containing the copper of Cu > 30%.
The present invention is suitable for processing waste lead accumulator containing lead plaster mud, and its quality percentage composition is (wt %): S content is less than 10, and Pb is 70 ~ 85.
The present invention and traditional waste lead accumulator are containing the comparison of lead plaster mud treatment process, there is following advantage: 1 for traditional pyrogenic processing method, the present invention is by controlling reducing atmosphere, in output lead bullion, utilize the reaction of Salmon-Saxl in cupric slag charge and waste lead accumulator, obtain the enriched substance copper matte regulus of copper and sulphur, realized the direct recovery of lead, copper and sulphur; The rate of recovery of 2 lead bullion of the present invention is greater than 98%, and the comprehensive recovery of copper and sulphur is greater than 95%, SO in flue dust
2concentration is reduced to below 1%, thereby has alleviated SO in traditional retailoring process
2improvement burden; 3 for conventional wet treatment process, and the reagent cost that the method adopts is lower, and operation is simple, and processing power is larger; 4 labour intensity of the present invention are low, the treatment time is short.
Embodiment
Embodiment 1:
Waste lead accumulator containing the main component of lead plaster mud is: S4.82%, Pb78.19%; The main component of iron ore is Fe 32.55%, SiO
28.98%, CaO 10.15%, Al
2o
34.02%; Industrial oxygen, wherein O
2content>=99%; Its SiO of quartz sand
2content 96%; Its CaO content of Wingdale is 53.26%; The main component of fine coal is C76.08%; Copper is bessemerized slag containing Cu 36.20%, and FeO 8.40%, SiO
26.50%.
By above-mentioned waste lead accumulator containing lead plaster mud and fine coal, bessemerize slag, iron ore, Wingdale and quartz sand and prepare burden, fine coal is respectively 15.2% and 26.8% of waste lead accumulator cream mud weight with the add-on of bessemerizing slag, the gross weight amount of the iron ore adding, Wingdale, quartz sand be waste lead accumulator contain lead plaster mud weight 30%, the smelting slag type after batching is FeO and SiO
2weight ratio is 1.44:1, CaO and SiO
2weight ratio is 0.71:1.
Add drum pelletizer to granulate mixed above-mentioned material; control furnace size is 10mm, moisture 6%; join in smelting furnace, simultaneously at 1200 ℃, blast 38% oxygen-rich air and carry out melting, the oxygen-rich air volume passing into and the weight ratio (m that enters stove furnace charge
3: kg) be 0.90:1, after melting 60min, emit successively matte, lead bullion and smelting slag.Gained lead bullion is leaded 97.8%, and lead recovery is 98.6%, the matte cupric 42% of output, and the comprehensive recovery of copper and sulphur is 96.2%, the flue dust of output is SO after cooling dedusting
2concentration is 0.6%, and the composition of the smelting slag of institute's output is: Pb 0.68%, and Cu 0.22%, and S 0.08%, and FeO 38.1%, SiO
226.6%, CaO 18.6%.
Embodiment 2:
Waste lead accumulator containing the main component of lead plaster mud is: S4.08%, Pb74.60%; The main component of iron ore is Fe 36.12%, SiO
27.09%, CaO 11.06%, Al
2o
35.04%; Industrial oxygen, wherein O
2content>=99%; The composition of lead bullion is: Pb98.2%; Its SiO of quartz sand
2content 96%; Its CaO content of Wingdale is 53.26%; The main component of coke is C78.05%; Copper refining slag is containing Cu 30.20%, and FeO 6.90%, SiO
216.50%.
Above-mentioned waste lead accumulator is prepared burden containing lead plaster mud and coke, copper refining slag, iron ore, Wingdale and quartz sand, the add-on of coke and copper refining slag is respectively 17.4% and 28.0% of waste lead accumulator cream mud weight, the gross weight amount of the iron ore adding, Wingdale, quartz sand be waste lead accumulator contain lead plaster mud weight 38%, the smelting slag type after batching is FeO and SiO
2weight ratio is 1.43:1, CaO and SiO
2weight ratio is 0.6:1.
Add drum pelletizer to granulate mixed above-mentioned material; control furnace size is 10mm, moisture 7.5%; join in smelting furnace, simultaneously at 1200 ℃, blast 40% oxygen-rich air and carry out melting, the oxygen-rich air volume passing into and the weight ratio (m that enters stove furnace charge
3: kg) be 0.96:1, after melting 60min, emit successively matte, lead bullion and smelting slag.Gained lead bullion is leaded 97.1%, and lead recovery is 98.2%, the matte cupric 45% of output, and the comprehensive recovery of copper and sulphur is 95.9%, the flue dust of output is SO after cooling dedusting
2concentration is 0.4%, and the composition of the smelting slag of institute's output is: Pb 0.52 %, and Cu 0.20%, and S 0.07%,, FeO 40.8%, SiO
228.6%, CaO 17.0%.
Claims (2)
1. melting waste lead accumulator, containing a method for lead plaster mud, is characterized in that comprising the following steps:
A batching
By waste lead accumulator containing lead plaster mud and coke or fine coal, cupric slag charge, iron ore, Wingdale, quartz sand mix, coke or fine coal add-on be waste lead accumulator contain lead plaster mud weight 10% ~ 25%; The add-on of cupric slag charge is 5 ~ 10 times that waste lead accumulator contains sulphur weight in lead plaster mud; The Wingdale adding, quartz sand and iron ore meet smelting slag type and require as FeO and SiO
2weight ratio is 1.2 ~ 1.75:1, CaO and SiO
2weight ratio is 0.4 ~ 0.9:1; In gained mixture, Pb content is 15% ~ 60%;
B granulates
Mixture is added and in nodulizer, mixes and granulate, control amount of water, after mixing, obtaining granularity is 6 ~ 25mm, moisture 5% ~ 10% enter stove material;
C melting
To enter stove material joins and in smelting furnace, carries out retailoring, smelting temperature is controlled at 1100 ~ 1300 ℃, pass into volumetric concentration simultaneously and be 21% ~ 50% oxygen-rich air, the oxygen-rich air volume passing into is 0.6 ~ 1.2:1 with the envelope-bulk to weight ratio that enters the weight of stove material, volume unit is cubic meter, the weight unit that enters stove material for kilogram, after melting 30 ~ 90min, emit successively lead bullion, copper matte regulus and smelting slag; The flue dust producing in fusion process, after negative pressure is gathered dust and cooled, returns to pelletization.
2. melting waste lead accumulator as claimed in claim 1, containing the method for lead plaster mud, is characterized in that: the cupric slag charge described in steps A is bessemerized slag or copper refining slag for containing the copper of Cu > 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310721550.8A CN103695650B (en) | 2013-12-25 | 2013-12-25 | A kind of melting waste lead accumulator is containing the method for lead plaster mud |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310721550.8A CN103695650B (en) | 2013-12-25 | 2013-12-25 | A kind of melting waste lead accumulator is containing the method for lead plaster mud |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103695650A true CN103695650A (en) | 2014-04-02 |
| CN103695650B CN103695650B (en) | 2016-02-10 |
Family
ID=50357309
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937983A (en) * | 2014-04-16 | 2014-07-23 | 湖北金洋冶金股份有限公司 | Collaborative disposal method for leaded glass of waste cathode ray tubes and lead plaster of waste storage batteries |
| CN104674022A (en) * | 2014-12-22 | 2015-06-03 | 芜湖金龙模具锻造有限责任公司 | Solvent for crude lead smelting |
| CN104789778A (en) * | 2015-03-11 | 2015-07-22 | 长沙矿冶研究院有限责任公司 | Recovery treatment method for Mn containing waste batteries |
| CN105803205A (en) * | 2016-03-17 | 2016-07-27 | 安徽省华鑫铅业集团有限公司 | Smelting process for efficient and energy-saving secondary lead |
| CN105821214A (en) * | 2016-03-22 | 2016-08-03 | 安徽华铂再生资源科技有限公司 | High-purity energy-saving and environment-friendly regenerated lead smelting technique |
| CN106756088A (en) * | 2016-11-22 | 2017-05-31 | 云南驰宏锌锗股份有限公司 | A kind of method that Ausmelt stoves process scrap lead cream |
| CN106756087A (en) * | 2016-11-22 | 2017-05-31 | 云南驰宏锌锗股份有限公司 | A kind of method that top side melting processes scrap lead cream |
| CN108461849A (en) * | 2017-02-20 | 2018-08-28 | 中国瑞林工程技术有限公司 | The processing system of lead-acid battery and its application |
| CN109266865A (en) * | 2018-10-17 | 2019-01-25 | 湖北楚凯冶金有限公司 | A kind of smelting process of lead-acid accumulator lead plaster |
| CN112267022A (en) * | 2020-09-10 | 2021-01-26 | 安徽华铂再生资源科技有限公司 | Sulfuric acid diachylon smelting method based on waste lead storage battery |
| CN114318000A (en) * | 2021-12-09 | 2022-04-12 | 靖远高能环境新材料技术有限公司 | Resource utilization method for lead-containing hazardous waste |
| CN114381606A (en) * | 2021-12-01 | 2022-04-22 | 国投金城冶金有限责任公司 | Recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate product |
| CN115852162A (en) * | 2023-01-29 | 2023-03-28 | 中南大学 | Smelting method of high-zinc melt molten pool reduction furnace slag and zinc and application thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937983B (en) * | 2014-04-16 | 2016-03-16 | 湖北金洋冶金股份有限公司 | Useless cathode tube flint glass and used and scrapped battery lead plaster cooperative disposal method |
| CN103937983A (en) * | 2014-04-16 | 2014-07-23 | 湖北金洋冶金股份有限公司 | Collaborative disposal method for leaded glass of waste cathode ray tubes and lead plaster of waste storage batteries |
| CN104674022B (en) * | 2014-12-22 | 2018-12-04 | 芜湖金龙模具锻造有限责任公司 | A kind of lead smelt solvent |
| CN104674022A (en) * | 2014-12-22 | 2015-06-03 | 芜湖金龙模具锻造有限责任公司 | Solvent for crude lead smelting |
| CN104789778A (en) * | 2015-03-11 | 2015-07-22 | 长沙矿冶研究院有限责任公司 | Recovery treatment method for Mn containing waste batteries |
| CN105803205A (en) * | 2016-03-17 | 2016-07-27 | 安徽省华鑫铅业集团有限公司 | Smelting process for efficient and energy-saving secondary lead |
| CN105821214A (en) * | 2016-03-22 | 2016-08-03 | 安徽华铂再生资源科技有限公司 | High-purity energy-saving and environment-friendly regenerated lead smelting technique |
| CN106756088A (en) * | 2016-11-22 | 2017-05-31 | 云南驰宏锌锗股份有限公司 | A kind of method that Ausmelt stoves process scrap lead cream |
| CN106756087A (en) * | 2016-11-22 | 2017-05-31 | 云南驰宏锌锗股份有限公司 | A kind of method that top side melting processes scrap lead cream |
| CN106756088B (en) * | 2016-11-22 | 2018-09-04 | 云南驰宏锌锗股份有限公司 | A kind of method of Ausmelt stoves processing scrap lead cream |
| CN108461849A (en) * | 2017-02-20 | 2018-08-28 | 中国瑞林工程技术有限公司 | The processing system of lead-acid battery and its application |
| CN109266865A (en) * | 2018-10-17 | 2019-01-25 | 湖北楚凯冶金有限公司 | A kind of smelting process of lead-acid accumulator lead plaster |
| CN109266865B (en) * | 2018-10-17 | 2021-01-01 | 湖北楚凯冶金有限公司 | Smelting method of lead paste of lead-acid storage battery |
| CN112267022A (en) * | 2020-09-10 | 2021-01-26 | 安徽华铂再生资源科技有限公司 | Sulfuric acid diachylon smelting method based on waste lead storage battery |
| CN114381606A (en) * | 2021-12-01 | 2022-04-22 | 国投金城冶金有限责任公司 | Recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate product |
| CN114318000A (en) * | 2021-12-09 | 2022-04-12 | 靖远高能环境新材料技术有限公司 | Resource utilization method for lead-containing hazardous waste |
| CN115852162A (en) * | 2023-01-29 | 2023-03-28 | 中南大学 | Smelting method of high-zinc melt molten pool reduction furnace slag and zinc and application thereof |
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|---|---|
| CN103695650B (en) | 2016-02-10 |
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Address after: Yongzhou City, Hunan province 425600 stone Ningyuan County Tong Industrial Park Patentee after: Fujia comprehensive central Polytron Technologies Inc Address before: Yongzhou City, Hunan province 425600 stone Ningyuan County Tong Industrial Park Patentee before: YONGZHOU FUJIA NON-FERROUS METALS CO., LTD. |