CN102234821A - Method for recovering and preparing superfine lead powder, zinc powder and pure lead ingots and zinc ingots from lead- and zinc-containing materials - Google Patents
Method for recovering and preparing superfine lead powder, zinc powder and pure lead ingots and zinc ingots from lead- and zinc-containing materials Download PDFInfo
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Abstract
The invention provides a method for recovering and preparing superfine lead powder, zinc powder and pure lead ingots and zinc ingots from lead- and zinc-containing materials, which comprises the following steps of: crushing the lead- and zinc-containing materials, leaching by using an aqueous alkali, and preparing wet lead powder and a lead-free zinc solution by adopting an electrolysis method or a zinc powder reduction method according to the content ratio of the led to the zinc in supernate; electrolyzing the lead-free zinc solution, and depositing wet zinc powder on a cathode; and washing the wet lead powder and the wet zinc powder with water, dehydrating and drying by using reducing easily-volatilized liquid to obtain dried superfine lead powder and superfine zinc powder with different grain sizes, and recycling the liquid; or smelting the wet lead powder by covering strong base to obtain pure lead ingots, and smelting the wet zinc powder by covering a reducing agent to obtain pure zinc ingots. The process flow is simple, the method is convenient to implement, and after the lead- and zinc-containing materials are treated by the method, the superfine lead powder or the pure lead ingots and the superfine zinc powder or the pure zinc ingots can be directly obtained at one time. The whole process of the technology is pollution-free, and the method has good economic benefit and is suitable for large-scale industrial production.
Description
[technical field]
The present invention relates to inorganic chemical industry and waste recovery processing technology field, relate in particular to a kind of to reclaim the method for producing ultra-fine lead powder zinc powder and pure lead pig zinc ingot metal in the leaded zinc material.
[background technology]
To the flue dust of smeltery's generation and/or the improvement of slag is the major issue that smelter faces, because words of its discarded discharging are not only wasted resource, also can cause environmental pollution.At present, many factories, R﹠D institution and the industry relevant personnel are putting forth effort to research and solve this problem, the zincy lead dust or the slag the like waste material that are produced in the hope of efficiently utilizing the smeltery, and improve its comprehensive added value, reduce environmental pollution, economize on resources.
At present, both at home and abroad smelting enterprise or refuse material to reclaim processing treatment enterprise be that the main method that raw material reclaims metallic lead, zinc is to adopt " pyrogenic attack technology " with smeltery's flue dust, slag the like waste.And over past ten years, what the zinc smelting industry adopted usually is that Zinc hydrometallurgy process carries out large-scale commercial production, and the pressurization of ten thousand tons of scales of zinc ore concentrate is leached the smeltery and built completion.The direct normal pressure agitation leach of the zinc ore concentrate of 100,000 t/a scales technology put into production in 2009 at home.
Yet no matter be " pyrogenic attack ", still " hydrometallurgy " all can not the direct production ultrafine powder.
Chinese patent literature CN1524652A discloses the method that a kind of vacuum arc method prepares ultra-fine lead powder, but its energy consumption height is unfavorable for industrialization.Chinese patent literature CN1817518A discloses a kind of method of producing metal zinc with zinc powder dirt or zinc dross, with strong base solution leaching zincilate material, filtering the back precipitates lead with sodium sulphite etc., electrolytic deposition obtains zinc powder again, its operation steps is many, lead in the zincilate material is separated can only be as the plumbous raw material of refining, can not be directly as product.And Chinese patent literature CN1524652A the method that a kind of vacuum arc method prepares ultra-fine lead powder also disclosed, but its energy consumption height is unfavorable for industrialization.
[summary of the invention]
The objective of the invention is to overcome the deficiency of existing production method and technical process, provide a kind of to reclaim the method for producing ultra-fine lead powder zinc powder and pure lead pig zinc ingot metal in the leaded zinc waste material in smeltery.This method technical process is simple, easy to operate, and it is pollution-free to handle the zincy lead material, can disposablely directly obtain ultra-fine lead powder or pure lead pig and super-fine zinc dust or pure zinc ingot.
To achieve the above object of the invention, the present invention proposes following technical scheme:
Reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in a kind of smeltery, comprise the steps:
S1 through pulverizing, leaches leaded zinc material with alkaline solution, obtain supernatant liquid and underflow solid;
S2 gets supernatant liquid and adopts electrolytic process or the wet lead powder of zinc powder reduction method preparation, obtains unleaded zinc liquid simultaneously;
The unleaded zinc liquid of S3 electrolysis, deposition obtains wet zinc powder on negative electrode, and obtains alkali lye;
S4 with the washing of reductibility volatile liquid, dehydrates aforementioned wet lead powder that makes and the washing of wet zinc powder again, makes ultra-fine lead powder and super-fine zinc dust.
Reclaim in the leaded zinc waste material in above-mentioned smeltery in the method for the ultra-fine lead powder zinc powder of preparation, in step S2, when zinc in the supernatant liquid that pre-treatment obtains: plumbous mass ratio adopts the wet lead powder of zinc dust precipitation reduction method preparation during less than 8: 1, obtains unleaded zinc liquid simultaneously.
Reclaim in the leaded zinc waste material in above-mentioned smeltery in the method for the ultra-fine lead powder zinc powder of preparation, the processing condition of the wet lead powder of described zinc dust precipitation reduction method preparation are: displacement stirring intensity: 1～3000 rev/min; Time swap: 1～10000 minute; Displacement temperature :-20～120 ℃; Displacement progression: 1～100 grade; Zinc powder consumption: 0.1～500 times of protective value; Zinc powder particle diameter: 0.1 micron～10 millimeters.
Reclaim in the leaded zinc waste material in above-mentioned smeltery in the method for the ultra-fine lead powder zinc powder of preparation, in step S2, when zinc in the supernatant liquid that pre-treatment obtains: plumbous mass ratio adopts the wet lead powder of electrolytic method preparation during greater than 10: 1, obtains unleaded zinc liquid simultaneously.
Reclaim in the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in above-mentioned smeltery, in step S2, zinc in the supernatant liquid that pre-treatment obtains: plumbous mass ratio is in [8～10]: in the time of 1, adopt the wet lead powder of electrolytic method or zinc dust precipitation reduction method preparation, obtain unleaded zinc liquid simultaneously.
Reclaim in the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in above-mentioned smeltery, among the step S4, the wet lead powder that will make earlier, wet zinc powder are respectively with 1～100 times washing, use 1～100 times dehydrated alcohol, alkane, aldehyde, ketone, benzene or tetracol phenixin reductibility easy volatile solvent wash again, dehydrate the back and obtain ultra-fine lead powder and super-fine zinc dust.
Reclaim in the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in above-mentioned smeltery, also comprise the underflow solid among the step S1 is reclaimed as the Rotary Kiln raw material, and/or alkali lye and the elutant among the step S4 that obtains among the step S3 reclaimed circulation as leaching liquid.
The present invention also provides the method that reclaims the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in a kind of smeltery, comprises the steps:
S1 through pulverizing, leaches leaded zinc material with alkaline solution, obtain supernatant liquid and underflow solid;
S2 gets supernatant liquid and adopts electrolytic process or the wet lead powder of zinc powder reduction method preparation, obtains unleaded zinc liquid simultaneously;
The unleaded zinc liquid of S3 electrolysis, deposition obtains wet zinc powder on negative electrode, and obtains alkali lye;
The S4 lead powder that will wet adopts highly basic to cover melting to make pure lead pig, and the alkaline residue circulation is leached; The zinc powder that will wet adopts coal dust or gac to cover melting and makes pure zinc ingot.
Reclaim in the method for the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in above-mentioned smeltery, in step S4, the lead powder cake of press that will wet, in plumbous cake and hydrogen-oxygen sodium solid masses than [0.1～100]: 1 ratio, cover plumbous cake surface with the fusion of hydrogen-oxygen sodium solid, melting makes pure lead pig.
Reclaim in the method for the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in above-mentioned smeltery, in step S4, the zinc powder cake of press that will wet is in zinc cake and coal dust or activated carbon mass ratio [0.1～100]: 1 ratio, cover zinc cake surface with coal dust or activated carbon, melting makes pure zinc ingot.
As can be seen from the above technical solutions, the method that from the leaded zinc waste material in smeltery, reclaims the ultra-fine lead powder zinc powder of preparation provided by the invention, its technical process is simple, easy to operate, it is pollution-free to handle the zincy lead material, can disposablely directly obtain ultra-fine lead powder and super-fine zinc dust, simultaneously more can make pure lead pig and pure zinc ingot, this be at present other in the processing of the leaded zinc waste material in smeltery can not reach.The better economic benefit of production method provided by the present invention is suitable for large-scale industrial production.
[description of drawings]
Shown in Figure 1 is the process flow sheet that reclaims the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery provided by the present invention;
Shown in Figure 2 is the process flow sheet that reclaims the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in smeltery provided by the present invention.
[embodiment]
Below with embodiment the present invention is described, but embodiment does not constitute any restriction of the present invention.
Embodiment 1
100 kilograms of the blast furnace dusts of certain iron work.Its principal element content is: zinc 16.19%, lead 1.13%, manganese 1.21%.Material is pulverized, added 800 liters of 480 grams per liter aqueous sodium hydroxide solutions, stirs and add 6 gram polyacrylamide flocculants after 30 minutes, separation obtaining 800 liters of supernatant liquors after the sedimentation.With supernatant liquid filtering, filter residue reclaims metal as raw materials for metallurgy.The filtrate that obtains is inserted electrolyzer, and at voltage 2.2V--3V, current density is under the 20A/m2--30A/m2 condition, and through the electrolysis of level Four electrolyzer, electrolytic solution flows in each electrolyzer voluntarily, and flow is 1L/s, and liquid circulation is used after the electrolysis.In the electrolytic process, every 20 minutes electrolyzer is brushed a plate, the lead powder under the brush flow in the collection powder groove with electrolytic solution and obtains 2.63 kilograms in ultra-fine wet lead powder.Improve voltage to 3.2 volt control current density 500 amperes per square meter, electrolysis scrapes 17.40 kilograms of ultra-fine wet zinc powders after 2 hours.
Gained wets lead powder, wet zinc powder respectively through washing, uses reductibility volatile solvent such as absolute ethanol washing again.Obtain 0.93 kilogram of ultra-fine lead powder after the drying, 15.11 kilograms of super-fine zinc dusts, this ultrafine powder is all by 325 mesh sieves.Resulting ultra-fine lead powder, wherein plumbous purity 〉=99.8% is applied to battery industry, can greatly increase the charging capacity of store battery or reduce the store battery volume, reduces the usage quantity of lead powder.Gained super-fine zinc dust wherein zinc total content is 99.35%, and metallic zinc content is 97.83% to meet market to the zinc powder requirement.
Alkali lye after the electrolysis is used for degree of depth leaching and isolates underflow thing after the supernatant liquor, and the mixture separation after the leaching goes out supernatant liquor and recycles as the leaching raw material, its underflow thing press filtration, and filtrate is as the leaching raw material, and filter residue reclaims metal as raw materials for metallurgy.
Embodiment 2
100 kilograms of certain plumbous zinc ore slags.Its principal element content is: zinc 30%, plumbous 12%.Material is pulverized, added 2000 liters of 500 grams per liter aqueous sodium hydroxide solutions, stirs and add 6 after 130 minutes and restrain polyacrylamide flocculants, separate after the sedimentation.Get 2000 liters of supernatant liquors, zinc 13.08g/L, plumbous 4.41g/L.Add 3.3 kilograms of displacements of zinc powder reduce spongy lead, the spongy lead cake of press is got 11 kilograms of plumbous cakes.Cover plumbous cake surface with the fusion of 11 kilograms of hydrogen-oxygen sodium solids, melting gets 8.825 kilograms of pure lead pigs, 0.55 kilogram of high-temperature vapor, and 12.625 kilograms of circulations of alkaline residue are leached.
2000 liters of unleaded zinc liquid after the displacement (zinc 14.65g/L), voltage are 3.2 volts of control current density 500 amperes per square meter, and electrolysis scrapes 30 kilograms of ultra-fine wet zinc powders after 2 hours.Solution after the electrolysis (zinc content is less than 5g/L), circulation is leached.Get 15 kilograms of wet zinc powders of gained through washing, wash with reductibility volatile solvent such as benzene, obtain 9.9 kilograms of super-fine zinc dusts after the drying, this ultrafine powder is all by 325 mesh sieves.Resulting ultra-fine lead powder, gained super-fine zinc dust wherein zinc total content are 98.67%, and metallic zinc content is 93.33%, meet market to the zinc powder requirement.
With 15 kilograms of ultra-fine wet zinc powder cake of press, get 8.8 kilograms of pure zinc ingots with the melting of coal dust covering surfaces, get smelting slag and make the Rotary Kiln raw material for 3.3 kilograms.
Embodiment 3
50 kilograms of certain plumbous zinc oxidized ores.Its principal element content is: zinc 60%, plumbous 24%.Material is pulverized, added 2000 liters of 500 grams per liter aqueous sodium hydroxide solutions, stirs and add 6 after 130 minutes and restrain polyacrylamide flocculants, separate after the sedimentation.Get 2000 liters of supernatant liquors, zinc 13.08g/L, plumbous 4.41g/L.Add 3.3 kilograms of displacements of zinc powder reduce spongy lead, the spongy lead cake of press is got 11 kilograms of plumbous cakes.Cover plumbous cake surface with the fusion of 11 kilograms of hydrogen-oxygen sodium solids, melting gets 8.825 kilograms of pure lead pigs, 0.55 kilogram of high-temperature vapor, and 12.625 kilograms of circulations of alkaline residue are leached.
2000 liters of unleaded zinc liquid after the displacement (zinc 14.65g/L), voltage are 3.2 volts of control current density 500 amperes per square meter, and electrolysis scrapes 30 kilograms of ultra-fine wet zinc powders after 2 hours.Solution after the electrolysis (zinc content is less than 5g/L), circulation is leached.Get 15 kilograms of wet zinc powders of gained through washing, use reductibility volatile solvent such as heptane wash again, obtain 9.9 kilograms of super-fine zinc dusts after the drying, this ultrafine powder is all by 325 mesh sieves.Resulting ultra-fine lead powder, gained super-fine zinc dust wherein zinc total content are 98.67%, and metallic zinc content is 93.33%, meet market to the zinc powder requirement.
With 15 kilograms of ultra-fine wet zinc powder cake of press, get 8.8 kilograms of pure zinc ingots with the melting of coal dust covering surfaces, get smelting slag and make the Rotary Kiln raw material for 3.3 kilograms.
Embodiment 4
100 kilograms in certain plumbous zinc oxide waste material.Its principal element content is: zinc 32.41%, lead 2.41%, manganese 1.21%.Material is pulverized, added 1600 liters of 480 grams per liter aqueous sodium hydroxide solutions, stirs and add 6 gram polyacrylamide flocculants after 30 minutes, separation obtaining 1600 liters of supernatant liquors after the sedimentation.With supernatant liquid filtering, filter residue reclaims metal as raw materials for metallurgy.The filtrate that obtains is inserted electrolyzer, and at voltage 2.2V--3V, current density is under the 20A/m2--30A/m2 condition, and through the electrolysis of level Four electrolyzer, electrolytic solution flows in each electrolyzer voluntarily, and flow is 1L/s, and liquid circulation is used after the electrolysis.In the electrolytic process, every 20 minutes electrolyzer is brushed a plate, the lead powder under the brush flow in the collection powder groove with electrolytic solution and obtains 5.25 kilograms in ultra-fine wet lead powder.Improve voltage to 3.2 volt control current density 500 amperes per square meter, electrolysis scrapes 34.89 kilograms of ultra-fine wet zinc powders after 2 hours.
Gained wets lead powder, wet zinc powder respectively through washing, uses reductibility volatile solvent such as washing with acetone again.Obtain 1.85 kilograms of ultra-fine lead powder after the drying, 30.23 kilograms of super-fine zinc dusts, this ultrafine powder is all by 325 mesh sieves.Resulting ultra-fine lead powder, wherein plumbous purity 〉=99.8% is applied to battery industry, can greatly increase the charging capacity of store battery or reduce the store battery volume, reduces the usage quantity of lead powder.Gained super-fine zinc dust wherein zinc total content is 99.35%, and metallic zinc content is 97.83% to meet market to the zinc powder requirement.
Alkali lye after the electrolysis is used for degree of depth leaching and isolates underflow thing after the supernatant liquor, and the mixture separation after the leaching goes out supernatant liquor and recycles as the leaching raw material, its underflow thing press filtration, and filtrate is as the leaching raw material, and filter residue reclaims metal as raw materials for metallurgy.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc material, comprise the steps:
S1 through pulverizing, leaches leaded zinc material with alkaline solution, obtain supernatant liquid and underflow solid;
S2 gets supernatant liquid and adopts electrolytic process or the wet lead powder of zinc powder reduction method preparation, obtains unleaded zinc liquid simultaneously;
The unleaded zinc liquid of S3 electrolysis, deposition obtains wet zinc powder on negative electrode, and obtains alkali lye;
S4 with the washing of reductibility volatile liquid, dehydrates aforementioned wet lead powder that makes and the washing of wet zinc powder again, makes ultra-fine lead powder and super-fine zinc dust.
2. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery according to claim 1, it is characterized in that, in step S2, when zinc in the supernatant liquid that pre-treatment obtains: plumbous mass ratio is during less than 8: 1, adopt the wet lead powder of zinc dust precipitation reduction method preparation, obtain unleaded zinc liquid simultaneously.
3. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery according to claim 2, it is characterized in that, the processing condition of the wet lead powder of described zinc dust precipitation reduction method preparation are: displacement stirring intensity: 1～3000 rev/min; Time swap: 1～10000 minute; Displacement temperature :-20～120 ℃; Displacement progression: 1～100 grade; Zinc powder consumption: 0.1～500 times of protective value; Zinc powder particle diameter: 0.1 micron～10 millimeters.
4. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery according to claim 1, it is characterized in that, in step S2, when zinc in the supernatant liquid that pre-treatment obtains: plumbous mass ratio is during greater than 10: 1, adopt the wet lead powder of electrolytic method preparation, obtain unleaded zinc liquid simultaneously.
5. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery according to claim 1, it is characterized in that, in step S2, zinc in the supernatant liquid that pre-treatment obtains: plumbous mass ratio is in [8～10]: in the time of 1, adopt the wet lead powder of electrolytic method or zinc dust precipitation reduction method preparation, obtain unleaded zinc liquid simultaneously.
6. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery according to claim 1, it is characterized in that, among the step S4, the wet lead powder that will make earlier, wet zinc powder are respectively with 1～100 times washing, use 1～100 times dehydrated alcohol, alkane, aldehyde, ketone, benzene or tetrachloro charcoal reductibility easy volatile solvent wash again, dehydrate the back and obtain ultra-fine lead powder and super-fine zinc dust.
7. reclaim the method for the ultra-fine lead powder zinc powder of preparation in the leaded zinc waste material in smeltery according to claim 1, it is characterized in that, also comprise the underflow solid among the step S1 is reclaimed as the Rotary Kiln raw material, and/or alkali lye and the elutant among the step S4 that obtains among the step S3 reclaimed circulation as leaching liquid.
8. reclaim the method for the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in smeltery, comprise the steps:
S1 through pulverizing, leaches leaded zinc material with alkaline solution, obtain supernatant liquid and underflow solid;
S2 gets supernatant liquid and adopts electrolytic process or the wet lead powder of zinc powder reduction method preparation, obtains unleaded zinc liquid simultaneously;
The unleaded zinc liquid of S3 electrolysis, deposition obtains wet zinc powder on negative electrode, and obtains alkali lye;
The S4 lead powder that will wet adopts highly basic to cover melting to make pure lead pig, and the alkaline residue circulation is leached; The zinc powder that will wet adopts coal dust or gac to cover melting and makes pure zinc ingot.
9. reclaim the method for the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in smeltery according to claim 8, it is characterized in that: in step S4, the lead powder cake of press will wet, in plumbous cake and hydrogen-oxygen sodium solid masses than [0.1～100]: 1 ratio, cover plumbous cake surface with the fusion of hydrogen-oxygen sodium solid, melting makes pure lead pig.
10. reclaim the method for the pure lead pig zinc ingot metal of preparation in the leaded zinc waste material in smeltery according to claim 8, it is characterized in that: in step S4, the zinc powder cake of press will wet, in zinc cake and coal dust or activated carbon mass ratio [0.1～100]: 1 ratio, cover zinc cake surface with coal dust or activated carbon, melting makes pure zinc ingot.
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| CN2010101592889A CN102234821A (en) | 2010-04-26 | 2010-04-26 | Method for recovering and preparing superfine lead powder, zinc powder and pure lead ingots and zinc ingots from lead- and zinc-containing materials |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101592889A CN102234821A (en) | 2010-04-26 | 2010-04-26 | Method for recovering and preparing superfine lead powder, zinc powder and pure lead ingots and zinc ingots from lead- and zinc-containing materials |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593602A (en) * | 2014-12-31 | 2015-05-06 | 上海第二工业大学 | Method for extracting metallic lead from alkaline leaching solution of waste lead-containing glass |
| CN105039691A (en) * | 2015-08-25 | 2015-11-11 | 四川华富宇科技有限责任公司 | Method for leaching low-grade lead-zinc oxide ores through electrooxidation and leaching device of method |
| CN111455183A (en) * | 2020-05-14 | 2020-07-28 | 沈阳鑫迪环境技术有限公司 | Method for purifying and recovering lead and zinc by waste tire cracking carbon black |
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| JPH11124636A (en) * | 1997-10-16 | 1999-05-11 | Dowa Mining Co Ltd | Treatment of zinc leaching residue |
| CN101314184A (en) * | 2007-05-29 | 2008-12-03 | 于军 | Method for recycling and preparing ultra-fine zinc dust from zinc dust containing material |
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| JPH11124636A (en) * | 1997-10-16 | 1999-05-11 | Dowa Mining Co Ltd | Treatment of zinc leaching residue |
| CN101314184A (en) * | 2007-05-29 | 2008-12-03 | 于军 | Method for recycling and preparing ultra-fine zinc dust from zinc dust containing material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593602A (en) * | 2014-12-31 | 2015-05-06 | 上海第二工业大学 | Method for extracting metallic lead from alkaline leaching solution of waste lead-containing glass |
| CN105039691A (en) * | 2015-08-25 | 2015-11-11 | 四川华富宇科技有限责任公司 | Method for leaching low-grade lead-zinc oxide ores through electrooxidation and leaching device of method |
| CN111455183A (en) * | 2020-05-14 | 2020-07-28 | 沈阳鑫迪环境技术有限公司 | Method for purifying and recovering lead and zinc by waste tire cracking carbon black |
| CN111455183B (en) * | 2020-05-14 | 2022-03-01 | 沈阳鑫迪环境技术有限公司 | Method for purifying and recovering lead and zinc by waste tire cracking carbon black |
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Application publication date: 20111109 |