CN101824544A - Comprehensive recovery method for smelted lead waste slag of blast furnace - Google Patents
Comprehensive recovery method for smelted lead waste slag of blast furnace Download PDFInfo
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Abstract
The invention relates to a comprehensive recovery method for smelted lead waste slag of a blast furnace, and relates to a metal waste slag recovery method. The method comprises the following steps of: grinding the smelted lead waste slag of the blast furnace into powder with a certain particle size; mixing the powder, coking coal powder, ferric chloride homologues and ingredients; curing and roasting the mixture; and carrying out chlorination reduction volatilization to obtain magnetic ferric oxide powder and mixed smoke dust, wherein the iron recovery rate of the magnetized iron powder subjected to magnetic separation is over 80 percent; the qualified iron ore powder with more than or equal to 60 percent of the iron content can be obtained; the ash and the smoke dust are respectively subjected to dust collection and water-cooling adsorption to extract lead, zinc, copper, tin, stibium and the like; and the recovery rate is over 90 percent. Through the comprehensive recovery method, valuable metals are regenerated by using the smelted lead waste slag; environment pollution can be managed; and the condition of scarcity of mineral resources in China is relieved.
Description
Technical field
The present invention relates to the recovery method of the recovery method of metal waste residue, particularly smelted lead waste slag of blast furnace.
Background technology
The smelted lead waste slag of blast furnace iron content accounts for 30% of slag total amount, and non-ferrous metal complex distribution and content are more.Before this, the applicant proposes a kind of method of handling pyrite cinder with " comprehensive recovering process of pyrite cinder " (patent No. ZL200510021005,3), be characterized in first ore grinding, through magnetic separation briquetting chloridizing volatilization roasting, obtain qualified iron ball group, and reclaim nonferrous metal product.But the smelted lead waste slag of blast furnace iron content is lacked than the pyrite cinder iron content, non-ferrous metal such as copper, lead, zinc, gold and silver and metal oxide be pyrite cinder content 2-4 doubly, handle the pyrite cinder recovery method if still adopt, even can reclaim non-ferrous metal, also be difficult to reclaim the ferrous metal resource by follow-up flow process.
Summary of the invention
The object of the invention is to enlarge pyrite cinder and reclaims the various adaptability of route, at the smelted lead waste slag of blast furnace metal recovery, a kind of both recyclable non-ferrous metal is provided, the comprehensive recovering process of recyclable again low levels ferrous metal resource, and the iron product that makes recovery satisfies iron-holder greater than 60% basic demand, becomes qualified fine iron breeze.
The present invention realizes by following steps and technology:
(1) smelted lead waste slag of blast furnace is through filtering thin slag and coking coal powder, ferrous chloride, the iron trichloride done of wet ball-milling, ammonium chloride is gone into cylinder batching post curing 24 hours, advance rotary kiln baking, must magnetize powdered iron ore and mix flue dust, wherein, Z 250 gets iron ore concentrate through magnetic separation, imports three sections wet dust collections and mix flue dust;
Do thin slag: coking coal powder: ferrous chloride: iron trichloride: the weight ammonium chloride ratio is: 100: 10～15: 4～8: 2～4: 2;
(2) three sections wet dust collection technologies comprise:
Volatile matter and contain reduced iron flue dust complex salt sour the liquid iron protochloride, return cylinder batching, and slurries enter following technology:
A. slurries are equipped with sodium-chlor and get the tin chloride precipitation, get precipitation of lead chloride after the slurries cooling;
B. dope filtration liquid with Z 250 replace copper sponge;
C. replace filtrate with getting zinc hydroxide with postprecipitation in the lime;
D. must contain ferrous, the calcium chloride solution of chlorination after the reduction of filtrate ammoniacal liquor, return the cylinder batching with adding hydrochloric acid with the dry dust collection powder.
Further be to add magnesium chloride in dried thin slag, coking coal powder and the chloride series thing batching in technology (1) to improve slag melting point, do thin slag: coking coal powder: ferrous chloride: iron trichloride: ammonium chloride: the magnesium chloride weight ratio is 100: 10～15: 4～8: 2～4: 2: 1～2.
Further be that the magnetization powdered iron ore that technology (1) goes out behind the rotary kiln is made the additional reductive agent of magnetic ferroferric oxide, water-cooled cooling again with sodium hydroxide.
In the described technology (1), waste grinding particle size after wet type overflow ball milling filters is 140～200 orders.
Described technology (1) is to adopt multistage magnetic separation Z 250 iron ore concentrate, and promptly first section magneticstrength is 800 Gausses, and two sections magneticstrengties are 1200～1600 Gausses.
The present invention will grind smelted lead waste slag of blast furnace to certain particle size and coking coal powder, chloride series thing batching, slaking, roasting, chlorination reduction and volatilization obtain magnetic iron oxide powder and mix flue dust, wherein, magnetization iron powder iron recovery＞80% after magnetic separation, can get the qualified powdered iron ore of iron content 〉=60%, pyrite cinder recovery technology is gathered dust respectively, water-cooled absorbs and ash content and flue dust still adopt, and extracts valuable elements such as lead, zinc, copper, tin, antimony, and its rate of recovery reaches more than 90%.The present invention is by changing pyrite slag for comprehensive recovery process, the technical scheme that proposition is supported mutually, connected each other, from the refining lead waste slag, reclaim martial ethiops and non-ferrous metal, tangible technology and economical effectiveness have been obtained, for utilizing lead waste slag ore resources regeneration valuable metal, administer the lead waste slag environmental pollution, alleviating the deficient situation of domestic Mineral resources has big positive effect.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Below further specify the present invention in conjunction with the accompanying drawings by embodiment.Embodiment comprises but does not limit the scope of the invention.
Embodiment
(1) technical process of the present invention
Embodiment 1:
1) at first refining lead blast furnace waste is carried out wet type overflow ball milling ore grinding to 160 order, the thin filtering filtrate of dreg slurry enters the liquid circulation, filter to collect and do thin slag, in doing thin slag, add ammonium chloride, ferrous chloride, iron trichloride, be equipped with reductive agent (coking coal powder) chlorination, slaking 24 hours again, go into rotary kiln baking, maturing temperature is 1200～1250 ℃, being beneficial to nonferrous metal oxides all volatilizees, also be beneficial to the magnetization of iron, make iron formation Z 250 in the breeze, temperature is greater than 400 ℃ of kiln discharges, employing recirculated water cooling must be reduced ore pulp.
Above-mentioned dried thin slag, chlorizating agent, reductive agent parts by weight are: 100: 10: 12.
2) will reduce ore pulp carries out weak magnetic beneficiation, magneticstrength 800 Gausses, concentrate A and chats, the chats ore pulp is carried out middle magnetic concentration, magneticstrength 1500 Gausses, concentrate B and mine tailing.Merge concentrate A and B, must do the smart powder product of qualified iron after the filtration.The mine tailing iron content can be made the silicate cement filler less than 30%.
3) rotary kiln gained flue dust and volatile matter are carried out two sections dry dust collections, must do flue dust and volatile matter.Wherein, dried flue dust is mainly reduced iron, adds hydrochloric acid and sends to production iron(ic) chloride as standby auxiliary material; Volatile matter gets slurries through three sections wet dust collections.
4) slurries get the tin chloride precipitation after adding the sodium-chlor filtration; Collect the sedimentary filtered liquid of tin chloride be cooled to refilter below 100 ℃ precipitation of lead chloride; Collecting the filtered liquid of precipitation of lead chloride replaces with above-mentioned Z 250 or dried flue dust, get the copper sponge precipitation, collecting the sedimentary filtered liquid c of copper sponge neutralizes with lime, get the zinc hydroxide precipitation, collect the sedimentary filtered liquid a of zinc hydroxide with ammoniacal liquor reduce ferric hydroxide precipitate, the filtered liquid c that collects ferric hydroxide precipitate returns the overflow ball milling and sizes mixing.
Embodiment 2:
1) at first refining lead blast furnace waste is carried out wet type overflow ball milling ore grinding to 200 order, the thin filtering filtrate of dreg slurry enters the liquid circulation, filter to collect and do thin slag, in doing thin slag, add ammonium chloride, ferrous chloride, iron trichloride, for the ferric metasilicate that prevents low softening temperature forms, add and join magnesium chloride and be oxidized to magnesium oxide to improve 50～100 ℃ of slag softening temperatures, be equipped with reductive agent (coking coal powder) chlorination reductase 12 4 hours again, go into rotary kiln baking, maturing temperature is 1200～1250 ℃, makes iron formation Z 250 in the breeze, and temperature is greater than 400 ℃ of kiln discharges, adopt recirculated water to add 1.5% (V/V) sodium hydroxide and replenish the reduction magnetic history, must reduce ore pulp.
Above-mentioned dried thin slag, chlorizating agent, magnesium chloride, reductive agent weight ratio are: 100: 12: 1.5: 10.
2) will reduce ore pulp carries out weak magnetic beneficiation, magneticstrength 800 Gausses, concentrate A and chats, the chats ore pulp is carried out middle magnetic concentration, magneticstrength 1400 Gausses, concentrate B and mine tailing.Merge concentrate A and B, must do the smart powder product of qualified iron after the filtration.The mine tailing iron content can be made the silicate cement filler less than 30%.
3) rotary kiln gained flue dust and volatile matter are carried out two sections dry dust collections, must do flue dust and volatile matter.Wherein, dried flue dust is mainly reduced iron, adds hydrochloric acid and sends to production iron(ic) chloride as standby auxiliary material; Volatile matter gets slurries through three sections wet dust collections.
4) slurries get the tin chloride precipitation after adding the sodium-chlor filtration; Collect the sedimentary filtered liquid of tin chloride be cooled to refilter below 100 ℃ precipitation of lead chloride; Collecting the filtered liquid of precipitation of lead chloride replaces with above-mentioned Z 250 or dried flue dust, get the copper sponge precipitation, collecting the sedimentary filtered liquid c of copper sponge neutralizes with lime, get the zinc hydroxide precipitation, collect the sedimentary filtered liquid a of zinc hydroxide with ammoniacal liquor reduce ferric hydroxide precipitate, the filtered liquid c that collects ferric hydroxide precipitate returns the overflow ball milling and sizes mixing.
Embodiment 3:
1) at first refining lead blast furnace waste is carried out wet type overflow ball milling ore grinding to 200 order, the thin filtering filtrate of dreg slurry enters the liquid circulation, filter to collect and do thin slag, in doing thin slag, add ammonium chloride, ferrous chloride, iron trichloride, for the ferric metasilicate that prevents low softening temperature forms, add and join magnesium chloride and be oxidized to magnesium oxide to improve 50～100 ℃ of slag softening temperatures, be equipped with reductive agent (coking coal powder) chlorination again, slaking 24 hours, go into rotary kiln baking, maturing temperature is 1200～1250 ℃, make iron formation Z 250 in the breeze, temperature adopts recirculated water to add 2% (V/V) sodium hydroxide and replenishes the reduction magnetic history greater than 400 ℃ of kiln discharges.Must reduce ore pulp.
Above-mentioned thin slag, chlorizating agent, the magnesium oxide done, the reductive agent ratio is: 100: 8: 1: 12.
2) will reduce ore pulp carries out weak magnetic beneficiation, magneticstrength 800 Gausses, concentrate A and chats, the chats ore pulp is carried out middle magnetic separation, magneticstrength 1500 Gausses, concentrate B and mine tailing; Merge concentrate A and B, must do the smart powder product of qualified iron after the filtration; The mine tailing iron content can be made the silicate cement filler less than 30%.
3) rotary kiln gained flue dust and volatile matter are carried out two sections dry dust collections, must be mainly the dried flue dust of reduced iron, add hydrochloric acid and send to and produce iron(ic) chloride and make standby auxiliary material.Volatile matter gets slurries through three sections wet dust collections.
4) slurries get the tin chloride precipitation after adding the sodium-chlor filtration; Collect the sedimentary filtered liquid of tin chloride be cooled to refilter below 100 ℃ precipitation of lead chloride; Collecting the filtered liquid of precipitation of lead chloride replaces with above-mentioned Z 250 or dried flue dust, get the copper sponge precipitation, collecting the sedimentary filtered liquid c of copper sponge neutralizes with lime, get the zinc hydroxide precipitation, collect the sedimentary filtered liquid a of zinc hydroxide with ammoniacal liquor reduce ferric hydroxide precipitate, the filtered liquid c that collects ferric hydroxide precipitate returns the overflow ball milling and sizes mixing.
(2) waste chlorination reduction of the present invention, roasting and magnetize the ferromagnetic technological effect that selects
Table 1 lead bullion blast furnace waste main chemical (%)
| ??Fe | ??S | ??As | ??SiO 2 | ??CaO | ??MgO | ??Pb | ??Zn |
| ??29-30 | ??1.0 | ??0.3 | ??23.2 | ??11.99 | ??2.12 | ??2.1 | ??3.89 |
| ??Cu | ??Sn | ??Ag | ??Mo | ??Au | ??In | ??Al 2O 3 | Hydride oxygen |
| ??0.17 | ??0.23 | ??34.4g/f | ??300g/f | ??0.2g/f | ??68.4g/f | ??2-4 | About 20 |
The result is comprehensively reclaimed in table 2 waste reduction chlorination, magnetizing roasting
(continuous table 2)
Table 3 magnetization breeze magnetic separation result
Claims (8)
1. the comprehensive recovering process of a smelted lead waste slag of blast furnace comprises following technology:
(1) smelted lead waste slag of blast furnace is through filtering thin slag and coking coal powder, ferrous chloride, the iron trichloride done of wet ball-milling, ammonium chloride is gone into cylinder batching post curing 24 hours, advance rotary kiln baking, must magnetize powdered iron ore and mix flue dust, wherein, Z 250 gets iron ore concentrate through magnetic separation, imports three sections wet dust collections and mix flue dust;
Do thin slag: coking coal powder: ferrous chloride: iron trichloride: the weight ammonium chloride ratio is: 100: 10～15: 4～8: 2～4: 2;
(2) three sections wet dust collection technologies comprise:
Volatile matter and contain reduced iron flue dust complex salt sour the liquid iron protochloride, return cylinder batching, and slurries enter following technology:
A. slurries are equipped with sodium-chlor and get the tin chloride precipitation, get precipitation of lead chloride after the slurries cooling;
B. dope filtration liquid with Z 250 replace copper sponge;
C. replace filtrate with getting zinc hydroxide with postprecipitation in the lime;
D. must contain ferrous, the calcium chloride solution of chlorination after the reduction of filtrate ammoniacal liquor, return the cylinder batching with adding hydrochloric acid with the dry dust collection powder.
2. the method for claim 1, it is characterized in that adding magnesium chloride in dried thin slag, coking coal powder and the chloride series thing batching in technology (1) improves slag melting point, do thin slag: coking coal powder: ferrous chloride: iron trichloride: ammonium chloride: the magnesium chloride weight ratio is 100: 10～15: 4～8: 2～4: 2: 1～2.
3. as claim 1,2 described methods, it is characterized in that the magnetization powdered iron ore that technology (1) goes out behind the rotary kiln is made the additional reductive agent of magnetic ferroferric oxide, water-cooled cooling again with sodium hydroxide.
4. as claim 1,2 described methods, it is characterized in that in technology (1) that waste grinding particle size after wet type overflow ball milling filters is 140～200 orders.
5. method as claimed in claim 3 is characterized in that in technology (1), and waste grinding particle size after wet type overflow ball milling filters is 140～200 orders.
6. as claim 1,2 described methods, it is characterized in that in technology (1) that adopt multistage magnetic separation Z 250 iron ore concentrate, promptly first section magneticstrength is 800 Gausses, two sections magneticstrengties are 1200～1600 Gausses.
7. method as claimed in claim 3 is characterized in that in technology (1), adopts multistage magnetic separation Z 250 iron ore concentrate, and promptly first section magneticstrength is 800 Gausses, and two sections magneticstrengties are 1200～1600 Gausses.
8. method as claimed in claim 4 is characterized in that in technology (1), adopts multistage magnetic separation Z 250 iron ore concentrate, and promptly first section magneticstrength is 800 Gausses, and two sections magneticstrengties are 1200～1600 Gausses.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392138A (en) * | 2011-11-07 | 2012-03-28 | 云南东昌金属加工有限公司 | Technological method for comprehensively recovering valued metal such as indium and germanium from lead-zinc smoke |
| CN103103357A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for drying, calcining and cooling metal slag material |
| CN104294032A (en) * | 2014-09-30 | 2015-01-21 | 池煊庆 | Comprehensive recovery method of gravity separation tailings of tin oxide ore |
| CN106006716A (en) * | 2016-07-01 | 2016-10-12 | 赫章县金川锌业有限公司 | Method for producing direct-method zinc oxide by utilizing belt type roasting machine |
| CN108384946A (en) * | 2018-03-16 | 2018-08-10 | 湖南腾驰环保科技有限公司 | A kind of leaded secondary material balling technique |
| CN111495588A (en) * | 2020-04-27 | 2020-08-07 | 汉源县伟业环保科技有限公司 | Method for recycling, reducing and harmlessly treating lead-zinc smelting slag |
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| JPS59166635A (en) * | 1983-03-11 | 1984-09-20 | Nippon Mining Co Ltd | Dust treatment |
| CN101157985A (en) * | 2007-09-25 | 2008-04-09 | 池煊庆 | Comprehensive reclaiming method for pyrite slag |
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2010
- 2010-04-12 CN CN2010101443719A patent/CN101824544B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59166635A (en) * | 1983-03-11 | 1984-09-20 | Nippon Mining Co Ltd | Dust treatment |
| CN101157985A (en) * | 2007-09-25 | 2008-04-09 | 池煊庆 | Comprehensive reclaiming method for pyrite slag |
Non-Patent Citations (1)
| Title |
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| 《江西有色金属》 20080630 何启贤，等 烟化处理铅锑鼓风炉渣回收锌铟的生产实践 29-32 1-8 第22卷, 第2期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392138A (en) * | 2011-11-07 | 2012-03-28 | 云南东昌金属加工有限公司 | Technological method for comprehensively recovering valued metal such as indium and germanium from lead-zinc smoke |
| CN102392138B (en) * | 2011-11-07 | 2013-04-03 | 云南东昌金属加工有限公司 | Technological method for comprehensively recovering valued metal such as indium and germanium from lead-zinc smoke |
| CN103103357A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for drying, calcining and cooling metal slag material |
| CN103103357B (en) * | 2012-11-23 | 2014-04-09 | 陈泉兴 | Method for drying, calcining and cooling metal slag material |
| CN104294032A (en) * | 2014-09-30 | 2015-01-21 | 池煊庆 | Comprehensive recovery method of gravity separation tailings of tin oxide ore |
| CN104294032B (en) * | 2014-09-30 | 2016-09-07 | 池煊庆 | The comprehensive recovering process of oxidation tin ore gravity tailings |
| CN106006716A (en) * | 2016-07-01 | 2016-10-12 | 赫章县金川锌业有限公司 | Method for producing direct-method zinc oxide by utilizing belt type roasting machine |
| CN108384946A (en) * | 2018-03-16 | 2018-08-10 | 湖南腾驰环保科技有限公司 | A kind of leaded secondary material balling technique |
| CN111495588A (en) * | 2020-04-27 | 2020-08-07 | 汉源县伟业环保科技有限公司 | Method for recycling, reducing and harmlessly treating lead-zinc smelting slag |
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Effective date of registration: 20210723 Address after: 651400 southwest of Laoguan village, Gejiu City, Honghe Hani and Yi Autonomous Prefecture, Yunnan Province (in Panda kapok company) Patentee after: Yunnan ruijiexin renewable resources comprehensive utilization Co.,Ltd. Address before: 610041 room 402, unit 3, No. 60, Jinli Middle Road, Chengdu, Sichuan Patentee before: Chi Xuanqing |