CN104975166A - Method for treating antimony sulfide concentrate through sulfide phase reductive transformation-ore dressing - Google Patents
Method for treating antimony sulfide concentrate through sulfide phase reductive transformation-ore dressing Download PDFInfo
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- CN104975166A CN104975166A CN201510385266.7A CN201510385266A CN104975166A CN 104975166 A CN104975166 A CN 104975166A CN 201510385266 A CN201510385266 A CN 201510385266A CN 104975166 A CN104975166 A CN 104975166A
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- antimony
- zinc oxide
- sulfide
- secondary zinc
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Abstract
The invention discloses a method for treating antimony sulfide concentrate through sulfide phase reductive transformation-ore dressing. According to the method, antimony sulfide concentrate and secondary zinc oxide undergo reductive transformation at a temperature no more than 950 DEG C so as to produce reductive transformation products--metallic antimony and zinc sulfide; and the reductive transformation products undergo reselection and flotation so as to separate metallic antimony from the antimony sulfide concentrate. The method has the characteristics of cleanness, low temperature and low carbon, eliminates a great amount of low-concentration SO2 flue gas pollution in traditional antimony pyrometallurgical smelting process, shortens antimony smelting flow, and greatly reduces energy consumption and improves economic benefit; the method can realize continuous production by using continuously-operating large-size conventional equipment like a rotary kiln and a multi-hearth furnace, and is capable of passingly treating secondary zinc oxide with high fluorine and chlorine contents so as to allow secondary zinc oxide to become high-quality zinc sulfide concentrate which is two times higher in price.
Description
Technical field
The present invention relates to a kind of sulfide thing and reduce the method for conversion-beneficiating method process stibnite concentrate mutually, belong to Non-ferrous Metallurgy field.
Background technology
Due to the special property of antimony compounds, to not yet adopting oxygen enrichment strengthening bath smelting so far, make the main smelting process of antimony still for having continued to use the blast furnace volatile smelting of five more than ten years, this technique has adaptability to raw material strong, be suitable for process higher-grade antimony concentrate, the advantages such as antimony straight gyrus yield is high, and the purer and throughput of needle antimony oxygen is large, but exist and produce a large amount of low concentration SO
2high and the fume amount of smoke pollution environment, energy consumption is large, the shortcomings such as dust collecting system is huge, and obviously, this technique has been not suitable with current requirement, must replace with clean, low-carbon (LC) and high efficient technology.
For a change this situation, from the seventies in last century, people carry out clean antimony regulus novel process and fundamental research always, within 1985, Tin Mine Mining Affairs Bureau builds up the antimony hydrometallurgy factory producing star metal 11kt scale per year, and successful tests, the advantage of alkaline wet antimony regulus is that antimony leaching yield is high, and negative electrode antimony quality is good, sulphur in raw material is recycled utilization, eliminates the harm of pyrogenic process " sulphur cigarette ".The shortcomings such as but it is low to there is current efficiency, power consumption is high, and alkaline consumption is high, production cost and running cost high.Therefore, this antimony hydrometallurgy factory only runs 1 year and has just stopped production.Do potassium cloride agent with antimony pentachloride, directly obtain industrial application by " chloride-hydrolysis " and " new chloride-hydrolysis " of antimony sulfide ore or lead-antimony concentrate antimony white and high purity antimony product respectively at 1987 and 1998." new chloride-hydrolysis " high-purity weisspiessglanz production line of 2000t/a scale runs in the mining industry of occasion state at present always.This technique has and reclaims sulphur with the form of sulfur residue, and eliminate the harm of pyrogenic process " sulphur cigarette ", metal recovery rate is high, and comprehensive utilization such as to make good use of at the advantage; But it is large and the large shortcoming of chlorine two must be used to hinder its extensive widespread use to there is wastewater discharge.Be in the antimony pyrometallurgical smelting novel procesies such as " reducing-matting smelting " and " low-temperature molten salt antimony regulus " of conceptual phase and there is feature that is clean, low-carbon (LC), but these two kinds of techniques need special smelting equipment, so not yet obtain industrial application." potassium cloride-diaphragm electrolysis " antimony hydrometallurgy technique has completed the commerical test of 1t antimony/d scale, and this technique does not have low concentration sulphur dioxide flue gas to discharge, and does not have discharge of wastewater yet, without chlorine; Energy consumption is low, and comprehensive utilization is made good use of, but this technique is suitable only for middle and small scale antimony smelter because of plant issue.
In addition, the secondary zinc oxide cigarette ash of China's iron and steel and the annual all outputs up to a million tons of coloured industry, these cigarette ashes are mostly fluorine-containing, chlorine is higher, and have to pass through multiple hearth furnace or rotary kiln vaporization at high temperature or remove fluorine and chlorine with neutralizing treatment, secondary zinc oxide can include zinc hydrometallurgy main flow in.
Summary of the invention
Exist for existing antimony pyrometallurgical smelting technique and produce a large amount of low concentration SO
2the problems such as smoke pollution environment, energy consumption are high, the object of the invention is to be to provide a kind of is that the sulfide thing of sulphur-fixing agent reduces conversion-beneficiating method mutually with secondary zinc oxide, the method can process stibnite concentrate on a large scale continuously, isolate metallic antimony and zinc sulfide concentrates, and clean, less energy-consumption, low-carbon (LC), meet demand of industrial production.
In order to realize technical purpose of the present invention, the invention provides a kind of sulfide thing and reduce the method for conversion-beneficiating method process stibnite concentrate mutually, the method first by stibnite concentrate and secondary zinc oxide when carbonaceous reductant exists, at≤950 DEG C of temperature, carry out reduction transform, generate metallic antimony and zinc sulphide reduction converted product, reduction converted product isolates metallic antimony and zinc sulfide concentrates by gravity treatment in conjunction with floatation process.
With the solid sulphur reagent of secondary zinc oxide in technical scheme of the present invention, stibnite concentrate carries out the low-temperature reduction conversion of≤950 DEG C under carbonaceous reductant exists, can realize fixing of sulphur well, the reduction such as the zinc sulphide obtained and metallic antimony converted product can realize being separated by existing gravity treatment and floatation process.
Sulfide thing of the present invention reduces the method for conversion-beneficiating method process stibnite concentrate mutually and also comprises in following preferred version.
Invert point of reducing in preferred scheme is preferably 700 ~ 950 DEG C.Under this temperature condition, be more conducive to antimony sulfide and zinc oxide and carbonaceous reductant the solid sulphur heterogeneous reaction of reduction occurs, metallic antimony and zinc sulphide are respectively liquid and solid-state, and carbonic acid gas and CO (carbon monoxide converter) gas discharge.
The transformation time that reduces in preferred scheme is 0.5 ~ 5h.
In preferred scheme, secondary zinc oxide is as sulphur-fixing agent, with Sb in stibnite concentrate
2s
3with change into Sb and FeS
2the molar weight changing into secondary zinc oxide needed for FeS is theoretical amount metering, and the consumption of secondary zinc oxide is 90 ~ 120% of theoretical amount.
The secondary zinc oxide adopted in preferred scheme is the secondary zinc oxide that fluorine and cl content are high, wherein Zn >=70%, Pb≤2%, namely the low-grade secondary zinc oxide cigarette ash of by-product in iron and steel and nonferrous metallurgy is adopted, in reduction conversion process, fluorine and chlorine are removed in passing, then by flotation, inferior secondary zinc oxide is converted into high-quality zinc sulfide concentrates; Traditionally, secondary zinc oxide through multiple hearth furnace or rotary kiln vaporization at high temperature or must remove fluorine with neutralizing treatment and chlorine rear can be used as zinc hydrometallurgy raw material.
In preferred scheme, carbonaceous reductant is coal dust and/or coke powder.
More preferably in scheme, the consumption of carbonaceous reductant is 5 ~ 20% of stibnite concentrate quality.
Conversion reaction of reducing in preferred scheme realizes in multiple hearth furnace or rotary kiln.The preferred multiple hearth furnace of the present invention or rotary kiln are easy to the operate continuously and the scale operation that realize technique.
The metallic antimony obtained in technical solution of the present invention and zinc sulphide reduction converted product carry out gravity treatment extraction metallic antimony after pulverizing, and gravity tailings carries out flotation output zinc sulfide concentrates.Gravity treatment and flotation are all classical ore-dressing techniques, can use for reference the gravity treatment of similar materials and flotation experience and technical data.
The chemical reaction carried out in technical scheme of the present invention:
Under temperature of reaction of the present invention, particularly when temperature is within the scope of 750 DEG C ~ 950 DEG C, the Sb in raw material
2s
3and mainly there is following reaction in ZnO in auxiliary material and carbonaceous reductant:
Sb
2S
3(l)+3ZnO(s)+3C(s)＝2Sb(l)+3ZnS(s)+3CO(g) (1)
Sb
2S
3(l)+3ZnO(s)+3/2C(s)＝2Sb(l)+3ZnS(s)+3/2CO
2(g) (2)
In above-mentioned reaction process, liquid antimony sulfide thing is converted into liquid metal antimony and solid-state zinc sulphide by solid oxide zinc and charcoal, releases carbon oxide gas simultaneously.
In addition, the sulphur that the phase decomposition of part pyrite is separated out also reacts with zinc oxide and generates zinc sulphide:
FeS
2(s)+ZnO(s)+C(s)＝FeS(s)+ZnS(s)+CO(g) (3)
FeS
2(s)+ZnO(s)+1/2C(s)＝FeS(s)+ZnS(s)+1/2CO
2(g) (4)
Hinge structure, beneficial effect of the present invention: the present invention is first using the poor quality of industrial by-product high fluorine chlorine secondary zinc oxide cigarette ash as solid sulphur reagent, the reduction simultaneously carrying out stibnite concentrate transforms and the de-fluorine and chlorine removal of volatilization, obtains metallic antimony and zinc sulphide reduction converted product.Technique of the present invention belongs to clean environment firendly, low-carbon (LC), less energy-consumption type stibium smelting technology, be characterized in apparent, do not need fused salt, temperature of reaction is low, process operation is simple, and reduction converting apparatus can adopt the main equipment of continuously-running conventional in existing technique, can meet large-scale commercial production requirement.
Accompanying drawing explanation
The thing that [Fig. 1] is process stibnite concentrate of the present invention reduces the technical process of conversion-beneficiating method mutually.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of the scope of restriction the claims in the present invention protection.
Embodiment 1
The composition (wt.%) containing golden stibnite concentrate as test raw material is: Sb37.21, Fe13.27, S30.60, Cu0.085, Pb0.18, Bi 0.026, As0.034, SiO
27.14, Al
2o
32.26, CaO0.079, Au 56.6g/t; The composition (wt.%) of sulphur-fixing agent secondary zinc oxide is: Zn74.06, Fe0.076, As0.84, Cu0.011, Pb0.81, F0.44, Cl0.38, SiO
20.5, CaO0.016; The chemical composition (wt.%) of reduction coal dust is: C82.33, S3.01, SiO
26.66, CaO0.83, Al
2o
34.81, MgO0.23.Take the stibnite concentrate 100g of mentioned component, zinc oxide fume dust 65g, coal dust 6g respectively, mix in rear loading plumbago crucible, put into electric furnace at 850 DEG C, reduce inversion of phases 2.0h, obtain inversion of phases product 154g after cooling, its main chemical compositions (wt.%) is: Sb24.16, Fe8.62, S19.87, Zn31.26, Pb0.35, F0.013, Cl0.029.The decreasing ratio of fluorine and chlorine is respectively 93% and 80%.XRD and material phase analysis illustrate, antimony thing is mainly metallic antimony mutually, accounts for 95.46% of total antimony, and zinc is mainly ZnS and FeS mutually with the thing of iron, accounts for 94.65% of total zinc amount.
Embodiment 2
Composition (wt.%) as the antimony sulfide ore of test raw material is: Sb55.55, S22.51, Fe0.55, SiO
221.31, Pb0.01, As0.02, CaO1.52, Al
2o
30.40, Au0.40g/t.
Take the stibnite concentrate 100g of mentioned component and secondary zinc oxide cigarette ash 65g, the coal dust 8g of embodiment 1, mix in rear loading plumbago crucible, put into electric furnace and react 1.0h at 875 DEG C, obtain inversion of phases product 153g after cooling, its main chemical compositions (wt.%) is: Sb36.31, S14.71, Zn31.46, Pb0.34, F0.0093, Cl0.019.The decreasing ratio of fluorine and chlorine is respectively 95% and 88%.XRD and material phase analysis illustrate, antimony thing is mainly metallic antimony mutually, account for 96.35% of total antimony, the thing of zinc is mainly ZnS mutually, account for 95.45% of total zinc amount.
Embodiment 3
Composition (wt.%) as the antimony sulfide ore of test raw material is: Sb48.15, S21.82, Fe2.46, SiO
216.94, Pb0.085, Zn0.018, As0.02, CaO0.69, Al
2o
32.16, Au0.31g/t.
Take the stibnite concentrate 100g of mentioned component and secondary zinc oxide cigarette ash 60g, the coal dust 10g of embodiment 1, mix in rear loading plumbago crucible, put into electric furnace and react 45min at 900 DEG C, obtain inversion of phases product 148g after cooling, its main chemical compositions (wt.%) is: Sb32.53, S14.74, Zn30.00, Fe1.66, Pb0.38, F0.0054, Cl0.012.The decreasing ratio of fluorine and chlorine is respectively 97% and 92%.XRD and material phase analysis illustrate, antimony thing is mainly metallic antimony mutually, account for 97.25% of total antimony, the thing of zinc is mainly ZnS mutually, account for 95.32% of total zinc amount.
Claims (8)
1. a sulfide thing reduces the method for conversion-beneficiating method process stibnite concentrate mutually, it is characterized in that, by stibnite concentrate and secondary zinc oxide when carbonaceous reductant exists, at≤950 DEG C of temperature, carry out reduction transform, generate metallic antimony and zinc sulphide reduction converted product, reduction converted product isolates metallic antimony and zinc sulfide concentrates by gravity treatment in conjunction with floatation process.
2. method according to claim 1, is characterized in that, described reduction invert point is 700 ~ 950 DEG C.
3. method according to claim 1 and 2, is characterized in that, described reduction transformation time is 0.5 ~ 5h.
4. method according to claim 1, is characterized in that, described secondary zinc oxide as sulphur-fixing agent, with Sb in stibnite concentrate
2s
3change into Sb and FeS completely
2the amount changing into secondary zinc oxide needed for FeS is completely theoretical amount metering, and the consumption of secondary zinc oxide is 90 ~ 120% of theoretical amount.
5. method according to claim 1, is characterized in that, described carbonaceous reductant is coal dust and/or coke powder.
6. method according to claim 1 or 5, it is characterized in that, the consumption of described carbonaceous reductant is 5 ~ 20% of stibnite concentrate quality.
7. the method according to claim 1 or 4, is characterized in that, described secondary zinc oxide is high fluorine chlorine secondary zinc oxide, wherein Zn >=70%, Pb≤2%.
8. method according to claim 1, is characterized in that, described reduction conversion reaction realizes in multiple hearth furnace or rotary kiln.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118158A (en) * | 2018-02-01 | 2018-06-05 | 长沙有色冶金设计研究院有限公司 | The method that valuable metal is extracted from vulcanized slag and blast furnace dust |
| CN108823429A (en) * | 2018-07-06 | 2018-11-16 | 六盘水中联工贸实业有限公司 | A kind of smelting process of low-grade sulfur-bearing zinc oxide ore |
| CN112028130A (en) * | 2020-08-12 | 2020-12-04 | 中南大学 | Preparation method of iron disulfide/antimony trisulfide mixed electrode material |
| CN113444875A (en) * | 2021-06-28 | 2021-09-28 | 贵州理工学院 | Resource utilization method for synergistic treatment of antimony sulfide concentrate and aluminum industrial waste residues |
| CN115228594A (en) * | 2022-07-25 | 2022-10-25 | 中南大学 | Flotation preactivating agent for antimony oxide ore and activation and flotation method thereof |
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| CN103173637A (en) * | 2013-03-06 | 2013-06-26 | 中南大学 | Antimony sulfide concentrate oxygen-enriched melting tank melting method and side-blown furnace |
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2015
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118158A (en) * | 2018-02-01 | 2018-06-05 | 长沙有色冶金设计研究院有限公司 | The method that valuable metal is extracted from vulcanized slag and blast furnace dust |
| CN108118158B (en) * | 2018-02-01 | 2020-04-21 | 长沙有色冶金设计研究院有限公司 | Method for extracting valuable metals from sulfide slag and blast furnace gas ash |
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| CN108823429B (en) * | 2018-07-06 | 2020-09-11 | 六盘水中联工贸实业有限公司 | Smelting method of low-grade sulfur-containing zinc oxide ore |
| CN112028130A (en) * | 2020-08-12 | 2020-12-04 | 中南大学 | Preparation method of iron disulfide/antimony trisulfide mixed electrode material |
| CN113444875A (en) * | 2021-06-28 | 2021-09-28 | 贵州理工学院 | Resource utilization method for synergistic treatment of antimony sulfide concentrate and aluminum industrial waste residues |
| CN113444875B (en) * | 2021-06-28 | 2022-11-29 | 贵州理工学院 | Resource utilization method for synergistic treatment of antimony sulfide concentrate and aluminum industrial waste residues |
| CN115228594A (en) * | 2022-07-25 | 2022-10-25 | 中南大学 | Flotation preactivating agent for antimony oxide ore and activation and flotation method thereof |
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