CN104313328B - Lead and the method for gold is reclaimed based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material - Google Patents
Lead and the method for gold is reclaimed based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material Download PDFInfo
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Abstract
The invention discloses and a kind of reclaim lead and the method for gold based on the solid sulfur melting bath melting of difficult-treating gold mine and lead containing sludge raw material reduction, the method be difficult-treating gold mine, lead-containing material, iron content sulphur-fixing agent and flux powder are mixed after, pelletize, dry, obtain pellet；After gained pellet mixes with charcoal reducing agent, join in oxygen bottom blown furnace, be passed through oxygen-enriched air and carry out melting, obtain smelting slag, lead bullion, ferrum sulfonium and flue gas；Gold and lead mainly reclaim from lead bullion, and gold recovery is more than 99%, and lead recovery is more than 95%；Smelting slag is as cement or the high silicon ingredient of building work；Empty after off-gas recovery valuable metal；Ferrum sulfonium, after fluidized bed roasting, reclaims scum, and SO 2 tail gas is used for antacid, it is achieved that the comprehensive reutilization of resource；The method is simple to operate, low cost, meets industrialized production.
Description
Technical field
The present invention relates to a kind of based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material recovery lead
With the method for gold, belong to gold mine technical field of smelting.
Background technology
At present, for when refining containing the complicated intractable Gold Concentrate under Normal Pressure such as arsenic, carbon containing, cupric, microfine parcel,
The refinement method used both at home and abroad mainly has: boiling oxidizing roasting method, pressure leaching pre-oxidation, the pre-oxygen of antibacterial
Change cyanidation gold-extracted method etc..But above several method exists, and pollution is big, cost requirement high, long processing period and right
The problems such as raw ore adaptability is low, and only it is conceived to the recovery of gold, and other generally existed in gold mine are had valency
Metal is seldom taken into account.Therefore, exploitation a kind of can efficiently, cleaning procedure reclaim in difficult-treating gold mine gold and comprehensive
Reclaiming wherein valuable metal, this becomes inexorable trend.
China is lead manufacturing country the biggest in the world, is also lead-acid storage battery production state the biggest in the world, every year simultaneously
Produce the lead-acid accumulator clay of more than 2,000,000 tons, be the main next of low-sulfur leaded secondary material raw material
Source, these clay are in addition to small part and concentrate of lead sulfide ore are arranged in pairs or groups and entered lead smelting system, and major part uses wet method to take off
Sulfur converts a reduction melting technique, and this technique exists wet desulphurization and consumes a large amount of reagent and produce a large amount of waste water, go back
Former melting is for being interrupted operation, and energy consumption is high, high in cost of production serious problems.Other lead secondary materials are as at non-ferrous metal
And in ferrimanganic metallurgical process produce multiple difficult lead secondary material, as lead fume ash, lead mud, sulphuric acid lead skim,
Useless storage battery smelting slag etc..Lead fume ash include secondary lead smelting flue dust, Lead Smelting in Blast Furnace flue dust, coper converter dust,
Lead copper matte processes flue dust, the leaded flue dust of manganese factory recovery, the leaded flue dust of steel mill's recovery；Lead mud drum includes leaded useless
Water processes mud, the sour mud of antacid tail gas spray trapping, lead factory rainwater and the mud of recirculated water collection produced；
Lead sulfate slag system hydrometallurgy waste residue, including sulfuric acid leaching slag, the high acidic oils of zinc hydrometallurgy factory of secondary zinc oxide
Slag, zine-smelting plant hyperbaric oxygen leaching slag select sulfur mine tailing.These lead secondary materials use reverberatory furnace or sintering drum mostly
Wind furnace local method is smelted, and equally exists pollution weight, the serious problems such as energy consumption is big.
Summary of the invention
The deficiency existed for the processing method of secondary material leaded to difficult-treating gold mine and low-sulfur in prior art,
It is an object of the invention to be to provide a kind of based on difficult-treating gold mine with lead containing sludge raw material by simple melting skill
Art efficient recovery gold and the method for lead, the method is simple to operate, low cost, it is achieved that the comprehensive of valuable resource returns
Receive and utilize, meet industrialized production.
The invention provides a kind of based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material recovery
Lead and the method for gold, the method comprises the following steps:
Step one: pelletize
By difficult-treating gold mine, lead-containing material, iron content sulphur-fixing agent and flux powder mix after, pelletize, be dried,
To pellet；Wherein, the quality of lead-containing material is the 30～60% of difficult-treating gold mine quality, adding of iron content sulphur-fixing agent
Entering amount is needed in ferrum sulphur-fixing agent, ferrum is completely converted into iron sulfide 1.0～2.0 times of theoretical molar amount, adding of flux
Entering amount makes pellet composition meet SiO2It is 0.8～1.2:1 with the mol ratio of FeO, SiO2With the mol ratio of CaO it is
1～2:1；Described lead-containing material is concentrate of lead sulfide ore, Zinc Hydrometallurgy Residue, leaded wet type copper smelting slag, plumbic acid storage
One or more in battery mud；Described iron content sulphur-fixing agent is iron oxide ore and/or pyrite cinder；Described
Flux be fluvial sand and/or limestone；
Step 2: melting
After step one gained pellet mixes with charcoal reducing agent, join in oxygen bottom blown furnace, be passed through oxygen-enriched air,
Melting under 900～1300 DEG C of high temperature, obtains smelting slag, lead bullion, ferrum sulfonium and flue gas；Wherein, oxygen-enriched air
Intake be 100～200Nm3Pellet per ton；In described oxygen-enriched air, oxygen volume content is 30～95%；
Described charcoal reducing agent quality is pellet mass 8～15%；
Step 3: electrolysis
Step 2 gained lead bullion passes through electrorefining, obtains lead bullion and the earth of positive pole containing gold.
The present invention reclaims lead and the side of gold based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material
Method also includes following preferred version:
Preferably in scheme, difficult-treating gold mine granularity is 0.02～1mm.
Preferably in scheme, lead-containing material granularity is 0.02～10mm.
Preferably in scheme, flux granularity is 1～20mm.
Preferably in scheme, charcoal reducing agent granularity is 5～25mm.
Preferably in scheme, charcoal reducing agent is fine coal and/or coking coal.
Preferably in scheme, in pellet, biodiversity percentage composition is 2～10%, and pellet particle diameter is 6～30mm.
Preferably in scheme, smelting temperature is 1100～1300 DEG C.
Preferably in scheme, smelting time is 30～120 minutes.
Preferably in scheme, step 2 gained ferrum sulfonium obtains scum and sulfur dioxide flue gas, scum after fluidized bed roasting
Returning step one process as iron content sulphur-fixing agent, SO 2 tail gas body enters acid making system and prepares sulphuric acid.
Preferably in scheme, step 2 gained flue gas removing dust empties after reclaiming valuable metal.
Preferably in scheme, step 2 gained smelting slag as cement or is built the high silicon ingredient of work and is used.
The creative main points of the present invention: through inventor numerous studies find, will contain arsenic, carbon containing, cupric,
The complicated difficult-treating gold mine such as microfine parcel under iron content sulphur-fixing agent effect, passes through suitably temperature with lead containing sludge raw material
Reduction melting under Du, effectively can dissociate lead and gold with other metal impurities, finally give lead gold
Alloy.Numerous studies show: difficult-treating gold mine, lead-containing material and iron content sulphur-fixing agent etc., in the reaction of the present invention
Under the conditions of, carry out a series of reaction: (1) ferrum oxide is reduced into ferrous oxide or metallic iron: Fe2O3+
CO=2FeO+CO2, Fe2O3+ 3CO=2Fe+CO2, lead sulfate reduction decomposition in (2) lead waste residue:
PbSO4+ 4CO=PbS+4CO2, the FeS that (3) desulfurization reaction produces forms ferrum ferrum sulfonium: FeS2+FeO+
CO=2FeS+CO2, 2FeS2=2FeS+S2, FeO+0.5S2+ CO=FeS+CO2, 4FeAsS+3O2
=4FeS+2As2O3, PbSO4+ FeO+CO=Pb+FeS+CO2, PbS+FeO+CO=Pb+
FeS+CO2, (4) lead oxide generation reduction reaction: PbO+CO=Pb+CO2, PbO2+ 2CO=Pb+
2CO2.By the fusion process of the present invention, the gold overwhelming majority enters in lead bullion, obtains after lead bullion electrorefining
Lead bullion and the earth of positive pole rich in gold, reclaim the valuable elements such as gold from the earth of positive pole；Ferrum and sulfur form ferrum sulfonium, little portion
The metal such as parting enters ferrum sulfonium, ferrum sulfonium after fluidized bed roasting, scum Returning smelting process, recycle ferrum and return
Receive gold, and tail gas is high sulfur dioxide gas, after waste heat boiler reclaims heat energy, by acid making system antacid；
Smelting slag is as cement or builds the high silicon ingredient of work and uses.Technical scheme achieve difficult-treating gold mine and
The common recovery of the valuable metal in lead waste residue, makes resource be fully used.
Compared to the prior art, the present invention have the beneficial effects that: 1, technical process is simple, low cost,
Can be with large-scale industrial production.2, gold recovery is more than 99%, and lead recovery is more than 95%；Smelting slag is made
For cement or the high silicon ingredient of building work；Empty after off-gas recovery valuable metal；After the calcining of ferrum sulfonium, reclaim scum,
Tail gas is used for antacid rich in sulfur dioxide, it is achieved that the comprehensive reutilization of resource, environmental protection and economy.
Accompanying drawing explanation
[Fig. 1] is the process chart of the present invention.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than limit the scope of the invention.
Embodiment 1
By high sulfur content gold mine (particle size range is 0.08～0.5mm), (particle size range is 0.05～5 to concentrate of lead sulfide ore
Mm), iron oxide ore (particle size range is 0.08～5mm) and limestone (particle size range is 2～15mm) powder
After the mixing of end, pelletize, to be dried to moisture be about 8%, obtains size and is about about 20mm
Pellet；Prepare pellet main component Pb21.01%, SiO211.86%, FeO11.67%, CaO5.27%,
S10.63%, Au10g/t.Gained pellet and coking coal (quality is the 14% of pellet mass, and particle diameter is 10～20mm)
After mixing, join in oxygen bottom blown furnace, with 180Nm3The speed of pellet per ton is passed through oxygen volumn concentration
It is the oxygen-enriched air of 35%, melting 50min under 1200～1300 DEG C of high temperature, obtain smelting slag, lead bullion, ferrum
Sulfonium and flue gas；In coarse-lead alloy containing gold 135g/t, gold enters alloy rate 99.2%, by electrorefining obtain lead and
Containing the earth of positive pole of gold, gold comprehensive recovery 99.8%, vertical yield reaches 84.75%, and the response rate is 98.64%.
Flue gas product is collected containing metal-oxide flue dust such as zinc through dedusting, containing SO2Concentration is less than 400ppm, reaches
Directly the requirement of emptying, reaches captured sulfur result.Ferrum sulfonium after high-boiling roasting, gained SO 2 tail gas
SO2Mass percent concentration is more than 18%, directly uses acid-making process antacid.Smelting slag is high silicon product, makees
For building work raw material.
Embodiment 2
By the gold mine (particle size range is 0.1～1mm) of high carbon content, Zinc Hydrometallurgy Residue (particle size range be 0.1～
10mm), iron oxide ore (particle size range is 1～10mm) and limestone (particle size range is 2～15mm) powder
After the mixing of end, pelletize, to be dried to moisture be about 10%, obtains size and is about about 15mm
Pellet；Prepare pellet main component Pb15.8%, SiO220.96%, FeO20.09%, CaO10.44%,
S20.3%, Au14g/t.Gained pellet and coking coal (quality is the 12% of pellet mass, and particle diameter is 15～25mm)
After mixing, join in oxygen bottom blown furnace, with 150Nm3The speed of pellet per ton is passed through oxygen volumn concentration
It is the oxygen-enriched air of 60%, melting 80min under 1150～1250 DEG C of high temperature, obtain smelting slag, lead bullion, ferrum
Sulfonium and flue gas；Containing gold 157g/t in coarse-lead alloy, gold enters alloy rate 99%, obtains lead by electrorefining and contains
The earth of positive pole of gold, gold comprehensive recovery 99.2%, vertical yield reaches 80.62%, and the response rate is 98.6%.Cigarette
Gas product is collected containing metal-oxide flue dust such as zinc through dedusting, containing SO2Concentration is less than 400ppm, reaches straight
Run in sky requirement, reach captured sulfur result.Ferrum sulfonium after high-boiling roasting, gained SO 2 tail gas SO2
Mass percent concentration is more than 18%, directly uses acid-making process antacid.Smelting slag is high silicon product, as building
Work raw material.
Embodiment 3
By the gold mine (particle size range is 0.05～1mm) containing arsenic, lead-acid accumulator mud (particle size range be 1～
10mm), pyrite cinder (particle size range is 1～10mm) and fluvial sand (particle size range is 5～15mm) powder
After the mixing of end, pelletize, to be dried to moisture be about 6%, obtains size and is about about 15mm
Pellet；Prepare pellet main component Pb18.30%, Zn13%, SiO219.23%, FeO21.93%,
CaO10.83%, S20.12%, As2%, Au15g/t.(quality is pellet mass to gained pellet with coking coal
10%, particle diameter is 10～25mm) mixing after, join in oxygen bottom blown furnace, with 180Nm3Pellet per ton
Speed be passed through the oxygen-enriched air that oxygen volumn concentration is 80%, melting under 1100～1200 DEG C of high temperature
50min, obtains smelting slag, lead bullion, ferrum sulfonium and flue gas；Containing gold 163g/t in coarse-lead alloy, gold enters alloy rate
99.3%, obtain lead and the earth of positive pole containing gold, gold comprehensive recovery 99.5%, vertical yield by electrorefining
Reaching 79.98%, the response rate is 98.4%.Flue gas product is collected containing metal-oxide flue dust such as zinc through dedusting,
Containing SO2Concentration is less than 400ppm, reaches the requirement directly emptied, reaches captured sulfur result.Ferrum sulfonium boils through high temperature
After rising roasting, gained SO 2 tail gas SO2Mass percent concentration is more than 18%, directly uses towerman
Skill antacid.Smelting slag is high silicon product, as cement raw material.
Claims (8)
1. reclaiming lead and the method for gold based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material, it is special
Levy and be, comprise the following steps:
Step one: pelletize
By difficult-treating gold mine, lead-containing material, iron content sulphur-fixing agent and flux powder mix after, pelletize, be dried,
To pellet；Wherein, the quality of lead-containing material is the 30～60% of difficult-treating gold mine quality, adding of iron content sulphur-fixing agent
Entering amount is needed in ferrum sulphur-fixing agent, ferrum is completely converted into iron sulfide 1.0～2.0 times of theoretical molar amount, adding of flux
Entering amount makes pellet composition meet SiO2It is 0.8～1.2:1 with the mol ratio of FeO, SiO2With the mol ratio of CaO it is
1～2:1；Described lead-containing material is concentrate of lead sulfide ore, Zinc Hydrometallurgy Residue, leaded wet type copper smelting slag, plumbic acid storage
One or more in battery mud；Described iron content sulphur-fixing agent is iron oxide ore and/or pyrite cinder；Described
Flux be fluvial sand and/or limestone；
Step 2: melting
After step one gained pellet mixes with charcoal reducing agent, join in oxygen bottom blown furnace, be passed through oxygen-enriched air,
Melting 30～120 minutes under 900～1300 DEG C of high temperature, obtain smelting slag, lead bullion, ferrum sulfonium and flue gas；Wherein,
The intake of oxygen-enriched air is 100～200Nm3Pellet per ton；In described oxygen-enriched air, oxygen volume content is
30～95%；Described charcoal reducing agent quality is pellet mass 8～15%；
Step 3: electrolysis
Step 2 gained lead bullion passes through electrorefining, obtains lead bullion and the earth of positive pole containing gold.
2. the method for claim 1, it is characterised in that described difficult-treating gold mine granularity is 0.02～1mm；
Described lead-containing material granularity is 0.02～10mm；Described flux granularity is 1～20mm.
3. the method for claim 1, it is characterised in that described charcoal reducing agent granularity is 5～25mm.
4. method as claimed in claim 3, it is characterised in that described charcoal reducing agent is fine coal and/or coking coal.
5. the method for claim 1, it is characterised in that in described pellet, biodiversity percentage composition is
2～10%, pellet particle diameter is 6～30mm.
6. the method for claim 1, it is characterised in that smelting temperature is 1100～1300 DEG C.
7. the method as described in any one of claim 1～6, it is characterised in that step 2 gained ferrum sulfonium is through boiling roasting
Obtaining scum and sulfur dioxide flue gas after burning, scum returns step one process, sulfur dioxide as iron content sulphur-fixing agent
Tail gas enters acid making system and prepares sulphuric acid.
8. the method for claim 1, it is characterised in that step 2 gained flue gas removing dust reclaims valency gold
Empty after genus.
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| CN105838902B (en) * | 2016-04-01 | 2017-12-15 | 北京工业大学 | A kind of method based on self-propagating reaction processing concentrate of lead sulfide ore |
| CN106119568A (en) * | 2016-08-23 | 2016-11-16 | 陈安民 | A kind of with difficult metallurgical fine powder the replacement high-copper of solvent, high silicon lead raw ore smelting process |
| CN106244822A (en) * | 2016-08-23 | 2016-12-21 | 庞荣花 | A kind of lead bullion that improves contains the high zinc lead raw ore smelting process of gold, silver amount |
| CN108342589B (en) * | 2018-02-25 | 2020-06-02 | 中南大学 | Method for feeding high-arsenic gold ore calcine into bottom-blowing reduction furnace of lead smelting system in thermal state |
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| CN110863218B (en) * | 2019-11-27 | 2021-11-30 | 东北大学 | Method for extracting gold by adopting molten salt electrolysis enrichment |
| CN112921184B (en) * | 2021-01-25 | 2022-07-26 | 江西齐劲材料有限公司 | Pyrometallurgical lead smelting device and process |
| CN113122723A (en) * | 2021-03-31 | 2021-07-16 | 河南科技大学 | Full recycling method of gold smelting red slag |
| CN117535520A (en) * | 2024-01-09 | 2024-02-09 | 北京高能时代环境技术股份有限公司 | Method for smelting matte by reducing and producing iron powder internal circulation reinforced lead-containing waste residues |
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| JP4470689B2 (en) * | 2004-10-29 | 2010-06-02 | 三菱マテリアル株式会社 | Indium recovery method using tin smelting |
| CN101255500B (en) * | 2008-04-02 | 2011-02-09 | 河南豫光金铅股份有限公司 | Smelting method for separating value metals from anode mud by firing process and device thereof |
| CN101514399B (en) * | 2009-04-03 | 2010-12-29 | 湖南宇腾有色金属股份有限公司 | Balancing lead smelting process for comprehensive resource utilization and device thereof |
| CN102312107A (en) * | 2011-08-30 | 2012-01-11 | 北京矿冶研究总院 | Smelting method of Carlin type gold ore |
| CN102965509A (en) * | 2012-11-27 | 2013-03-13 | 中南大学 | Method and device for treating daub and iron-rich heavy metal solid waste of waste lead-acid storage battery |
| CN103243221B (en) * | 2013-05-16 | 2014-04-30 | 中南大学 | Method for directly gathering gold by virtue of smelting of unmanageable gold ore molten pool containing arsenic and stibium |
| CN103266225A (en) * | 2013-05-26 | 2013-08-28 | 湖南宇腾有色金属股份有限公司 | Side-blown furnace reduction smelting technology for lead anode mud |
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