CN103695650B - A kind of melting waste lead accumulator is containing the method for lead plaster mud - Google Patents
A kind of melting waste lead accumulator is containing the method for lead plaster mud Download PDFInfo
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- CN103695650B CN103695650B CN201310721550.8A CN201310721550A CN103695650B CN 103695650 B CN103695650 B CN 103695650B CN 201310721550 A CN201310721550 A CN 201310721550A CN 103695650 B CN103695650 B CN 103695650B
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Abstract
Melting waste lead accumulator containing the method for lead plaster mud, by waste lead accumulator containing lead plaster mud and reductive agent coke or fine coal, cupric slag charge, iron ore, quartz sand, Wingdale mix.Coke or fine coal add-on are that waste lead accumulator contains 10% ~ 25% of lead plaster mud weight; Cupric slag charge is 5 ~ 10 times that waste lead accumulator contains sulphur weight in lead plaster mud; The Wingdale added, 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, join in cylinder or disk pelletizing machine and granulate, and the stove material that enters after granulation passes into oxygen-rich air retailoring in smelting furnace.The present invention, by controlling reducing atmosphere, while output lead bullion, utilizes the reaction of Salmon-Saxl in cupric slag charge and waste lead accumulator, obtains the enriched substance copper matte regulus of copper and sulphur, achieve the direct recovery of lead, copper and sulphur; The rate of recovery of lead bullion is greater than 98%, and the comprehensive recovery of copper and sulphur is greater 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 reclaimed, after being crushed to certain particle size, adopting the sorting such as waterpower or medium system produce vulcanite, plastics, lead antimony alloy particle and contains lead plaster mud, wherein mainly containing PbSO containing lead plaster mud
4, PbO
2, PbO and Pb etc., have pyrogenic process and wet method two kinds for the treatment of process from containing Footwall drift lead lead plaster mud at present.
Pyrometallurgical smelting containing lead plaster mud is generally the method adopting retailoring.The reductive agent that retailoring adopts is breeze, coal dust or iron filings, after lead plaster mud and the flux mix such as these reductive agents and Wingdale, river sand, sodium carbonate, adds in smelting furnace and 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, there is the shortcoming that smelting furnace efficiency of utilization is low, production energy consumption is high, containing low-concentration sulfur dioxide in the flue gas of simultaneously output, easily causes environmental pollution.The method process of oxygen enrichment refining lead is the new technology developed in recent years containing lead plaster mud, containing lead plaster mud and concentrate of lead sulfide ore, after the mixes such as sludging flux, add in smelting furnace and carry out oxidizing semlting, high-concentration oxygen is passed in fusion process, under the oxidation and stirring action of oxygen, violent cross reaction is at high temperature there is containing lead plaster mud and concentrate of lead sulfide ore, 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 then 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.The plumbous treatment process of oxygen enrichment refining has that throughput is large, plumbous 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 needs to maintain higher temperature of reaction due to fusion process, therefore, it is possible to provide the concentrate of lead sulfide ore allocation ratio of heat higher, often needs additionally add certain breeze or coal dust as auxiliary fuel simultaneously.
Wet treatment method containing lead plaster mud is then first carry out wet method conversion to containing lead plaster mud, adopt the transforming agents such as sodium carbonate, volatile salt or bicarbonate of ammonia will be converted into lead carbonate containing lead sulfate in lead plaster mud, be translated into yellow lead oxide under then selecting the condition of the reductive agents such as ammonium sulphite containing the plumbic oxide in lead plaster mud, the product obtained carries out retailoring output lead bullion or adopts the method for silicofluoric acid dissolving-galvanic deposit to reclaim plumbous.The method environmental friendliness, metal recovery rate is high, and there is main shortcoming is that throughput is little and production cost is higher.
Summary of the invention
In order to overcome the deficiency of above-mentioned process containing lead plaster mud, the invention provides the waste lead accumulator that a kind of comprehensive recovery is high, environmental friendliness, cost are low and containing lead plaster mud melting method.
The present invention be achieve the above object adopt technical scheme be: by waste lead accumulator containing lead plaster mud and reductive agent coke or fine coal, prepare burden according to certain ratio containing copper ashes, iron ore, quartz sand, Wingdale after; join in cylinder or disk pelletizing machine and granulate; material after granulation to join in smelting furnace and passes into oxygen-rich air and carries out retailoring, direct output lead bullion, copper matte regulus, smelting slag and flue dust.
The technological process that the present invention is concrete and technical parameter as follows:
1 batching
Prepared burden containing lead plaster mud and coke or fine coal, cupric slag charge, iron ore, Wingdale, quartz sand by waste lead accumulator, coke or fine coal add-on are that waste lead accumulator contains 10% ~ 25% of lead plaster mud weight; 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 added, 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 in nodulizer and carries out mixing and granulating, control amount of water, obtaining granularity after mixing is 6 ~ 25mm, moisture 5% ~ 10% enter stove material.
3 meltings
Stove material will be entered join in smelting furnace and carry out retailoring, smelting temperature controls at 1100 ~ 1300 DEG C, pass into the oxygen-rich air that volumetric concentration is 21% ~ 50% simultaneously, the oxygen-rich air volume passed into is 0.6 ~ 1.2:1 with the envelope-bulk to weight ratio of the weight entering stove material, volume unit is cubic meter, the weight unit entering stove material for kilogram, after melting 30 ~ 90min, release lead bullion, copper matte regulus and smelting slag successively.The flue dust produced in fusion process, after negative pressure is gathered dust and cooled, returns pelletization.The main chemical reactions occurred 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 added is containing CaO > 45%, and quartz sand is containing SiO
2>90%, iron ore iron content > 35%.
Described cupric slag charge is bessemerize slag or copper refining slag containing the copper of Cu > 30%.
The present invention is suitable for process waste lead accumulator containing lead plaster mud, and its mass percentage is (wt%): it is 70 ~ 85 that S content is less than 10, Pb.
The present invention compares containing lead plaster mud treatment process with traditional waste lead accumulator, there is following advantage: 1 for traditional pyrogenic processing method, the present invention is by controlling reducing atmosphere, while 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, achieve 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 less than 1%, thus alleviates 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 Fe32.55%, SiO
28.98%, CaO10.15%, 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 bessemerizes slag containing Cu36.20%, FeO8.40%, 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 added, Wingdale, quartz sand is that waste lead accumulator contains 30% of lead plaster mud weight, and 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.
Mixed above-mentioned material is added drum pelletizer granulate; control furnace size is 10mm, moisture 6%; join in smelting furnace, the oxygen-rich air simultaneously blasting 38% at 1200 DEG C carries out melting, the oxygen-rich air volume passed into and the weight ratio (m entering stove furnace charge
3: kg) be 0.90:1, after melting 60min, release matte, lead bullion and smelting slag successively.Gained lead bullion leaded 97.8%, lead recovery is 98.6%, the matte cupric 42% of output, and the comprehensive recovery of copper and sulphur is 96.2%, flue dust SO after cooling dedusting of output
2concentration is 0.6%, and the composition of the smelting slag of institute's output is: Pb0.68%, Cu0.22%, S0.08%, FeO38.1%, SiO
226.6%, CaO18.6%.
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 Fe36.12%, SiO
27.09%, CaO11.06%, 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 Cu30.20%, FeO6.90%, 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 added, Wingdale, quartz sand is that waste lead accumulator contains 38% of lead plaster mud weight, and 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.
Mixed above-mentioned material is added drum pelletizer granulate; control furnace size is 10mm, moisture 7.5%; join in smelting furnace, the oxygen-rich air simultaneously blasting 40% at 1200 DEG C carries out melting, the oxygen-rich air volume passed into and the weight ratio (m entering stove furnace charge
3: kg) be 0.96:1, after melting 60min, release matte, lead bullion and smelting slag successively.Gained lead bullion leaded 97.1%, lead recovery is 98.2%, the matte cupric 45% of output, and the comprehensive recovery of copper and sulphur is 95.9%, flue dust SO after cooling dedusting of output
2concentration is 0.4%, and the composition of the smelting slag of institute's output is: Pb0.52%, Cu0.20%, S0.07%, FeO40.8%, SiO
228.6%, CaO17.0%.
Claims (2)
1. melting waste lead accumulator is containing a method for lead plaster mud, it is characterized in that comprising the following steps:
A prepares burden
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 are that waste lead accumulator contains 10% ~ 25% of lead plaster mud weight; The add-on of cupric slag charge is 5 ~ 10 times that waste lead accumulator contains sulphur weight in lead plaster mud; The Wingdale added, 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 in nodulizer and carries out mixing and granulating, control amount of water, obtaining granularity after mixing is 6 ~ 25mm, moisture 5% ~ 10% enter stove material;
C melting
Stove material will be entered join in smelting furnace and carry out retailoring, smelting temperature controls at 1100 ~ 1300 DEG C, pass into the oxygen-rich air that volumetric concentration is 21% ~ 50% simultaneously, the oxygen-rich air volume passed into is 0.6 ~ 1.2:1 with the envelope-bulk to weight ratio of the weight entering stove material, volume unit is cubic meter, the weight unit entering stove material for kilogram, after melting 30 ~ 90min, release lead bullion, copper matte regulus and smelting slag successively; The flue dust produced in fusion process, after negative pressure is gathered dust and cooled, returns pelletization.
2. melting waste lead accumulator as claimed in claim 1 is containing the method for lead plaster mud, it is characterized in that: the cupric slag charge described in steps A is bessemerize slag or copper refining slag containing the copper of Cu > 30%.
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|---|---|---|---|
| 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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|---|---|---|---|
| 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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| Publication Number | Publication Date |
|---|---|
| CN103695650A CN103695650A (en) | 2014-04-02 |
| CN103695650B true CN103695650B (en) | 2016-02-10 |
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| 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 |
| 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 |
| CN104789778B (en) * | 2015-03-11 | 2017-09-12 | 长沙矿冶研究院有限责任公司 | A kind of recovery and treatment method of the old and useless battery containing Mn |
| CN105803205B (en) * | 2016-03-17 | 2017-10-20 | 安徽省华鑫铅业集团有限公司 | A kind of energy-efficient secondary lead smelting technique |
| CN105821214B (en) * | 2016-03-22 | 2017-08-25 | 安徽华铂再生资源科技有限公司 | Reviver high-purity energy-conserving and environment-protective smelting process |
| CN106756087B (en) * | 2016-11-22 | 2018-09-04 | 云南驰宏锌锗股份有限公司 | A kind of method of top side melting processing 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 |
| 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 |
| CN114381606B (en) * | 2021-12-01 | 2023-07-07 | 国投金城冶金有限责任公司 | Recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting |
| 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 |
| CN115852162B (en) * | 2023-01-29 | 2023-06-02 | 中南大学 | Smelting method of high zinc melt molten pool reducing slag and zinc and application thereof |
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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. |