CN104975166B - A kind of method that sulfide thing mutually reduces conversion beneficiating method processing stibnite concentrate - Google Patents
A kind of method that sulfide thing mutually reduces conversion beneficiating method processing stibnite concentrate Download PDFInfo
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- CN104975166B CN104975166B CN201510385266.7A CN201510385266A CN104975166B CN 104975166 B CN104975166 B CN 104975166B CN 201510385266 A CN201510385266 A CN 201510385266A CN 104975166 B CN104975166 B CN 104975166B
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Abstract
A kind of method that conversion beneficiating method processing stibnite concentrate is mutually reduced the invention discloses sulfide thing, this method is that stibnite concentrate and secondary zinc oxide are carried out into reduction conversion at a temperature of≤950 DEG C, metallic antimony and zinc sulphide reduction converted product are generated, reduction converted product isolates metallic antimony and zinc sulfide concentrates by gravity treatment combination floatation process.This method has the characteristics of cleaning, low temperature, low-carbon, can not only eliminate a large amount of low concentration SOs existing for traditional antimony pyrometallurgical smelting technique2The pollution of flue gas, and shorten antimony regulus flow, energy consumption is greatly reduced and increases economic efficiency, the large-scale conventional equipment that rotary kiln, multiple hearth furnace etc. can be used continuously to run, realize continuous production, this method can also handle the high secondary zinc oxide of fluorine chlorinity in passing, be allowed to be converted into price and double the high-quality zinc sulfide concentrates of the above.
Description
Technical field
The present invention relates to a kind of method that sulfide thing mutually reduces conversion-beneficiating method processing stibnite concentrate, belong to coloured
Metal metallurgy smelting field.
Background technology
Due to the special nature of antimonial, to not yet using oxygen-enriched reinforcing bath smelting so far so that the master of antimony
It is still to have continued to use the blast furnace volatile smelting of more than 50 years to take smelting process, the technique have it is strong to adaptability to raw material, suitable for place
Manage high-grade antimony concentrate, antimony straight gyrus high income, the advantages that needle antimony oxygen is purer and production capacity is big, but exist produce it is a large amount of low dense
Spend SO2The shortcomings of smoke pollution environment, high energy consumption and fume amount are big, and dust collecting system is huge, it is therefore apparent that the technique has been not suitable with
Current requirement, it is necessary to substituted with cleaning, low-carbon and high efficient technology.
To change this situation, from the seventies in last century, people carry out cleaning antimony regulus new technology and basic theory always
Research, Tin Mine Mining Affairs Bureau in 1985 build up the antimony hydrometallurgy factory for producing star metal 11kt scales per year, and successful tests, alkaline wet
The advantages of antimony regulus is antimony leaching rate height, and negative electrode antimony quality is good, and the sulphur in raw material is recycled utilization, eliminates the danger of pyrogenic process " sulphur cigarette "
Evil.But it is low current efficiency to be present, the shortcomings of power consumption is high, and alkaline consumption is high, production cost and running cost are high.Therefore, the wet method is refined
Antimony factory only runs 1 year and just stopped production.Potassium cloride agent is made with Antimony pentachloride, antimony is directly produced by antimony sulfide ore or lead-antimony concentrate
White and high purity antimony product " chloride-hydrolysis " and " new chloride-hydrolysis " obtained commercial Application respectively at 1987 and 1998.
" new chloride-hydrolysis " high-purity antimony oxide production line of 2000t/a scales is run in the mining industry of occasion state always at present.The technique has
Sulphur is reclaimed in the form of sulfur residue, eliminates the harm of pyrogenic process " sulphur cigarette ", metal recovery rate is high, the advantages that comprehensive utilization；But deposit
Wastewater discharge greatly and its extensive extensive use must be hindered using two big shortcoming of chlorine.It is in " going back for conceptual phase
The antimony pyrometallurgical smelting new technology such as former matte smelting " and " low-temperature molten salt antimony regulus " has the characteristics of cleaning, low-carbon, but both techniques need
Special smelting equipment is wanted, so not yet obtaining commercial Application." potassium cloride-diaphragm electrolysis " antimony hydrometallurgy technique has completed 1t
The commerical test of antimony/d scales, the technique do not have low concentration sulphur dioxide flue gas discharge, without discharge of wastewater, without chlorine yet；
Energy consumption is low, and comprehensively utilizes, but the technique is suitable only for middle and small scale antimony smelter because of plant issue.
In addition, China's steel and the secondary zinc oxide cigarette ash of annual all up to a million tons of the outputs of coloured industry, these cigarette ashes are mostly
It is fluorine-containing, chlorine is higher, it is necessary to by multiple hearth furnace or rotary kiln vaporization at high temperature or remove fluorine and chlorine, secondary zinc oxide with neutralizing treatment can
Include zinc hydrometallurgy main flow.
The content of the invention
Exist for existing antimony pyrometallurgical smelting technique and produce a large amount of low concentration SOs2The problems such as smoke pollution environment, high energy consumption, this
The purpose of invention is to be that providing a kind of sulfide thing using secondary zinc oxide as sulphur-fixing agent mutually reduces conversion-beneficiating method, this method
Can continuous processing stibnite concentrate on a large scale, isolate metallic antimony and zinc sulfide concentrates, and cleaning, low energy consumption, low-carbon, meet
Demand of industrial production.
In order to realize the technical purpose of the present invention, the invention provides a kind of sulfide thing mutually to reduce at conversion-beneficiating method
The method for managing stibnite concentrate, this method is first by stibnite concentrate and secondary zinc oxide in the presence of carbonaceous reductant, in≤950 DEG C
At a temperature of carry out reduction conversion, generate metallic antimony and zinc sulphide reduction converted product, reduction converted product combines floating by gravity treatment
Technique is selected to isolate metallic antimony and zinc sulfide concentrates.
Carried out in technical scheme with the solid sulphur reagent of secondary zinc oxide, stibnite concentrate in the presence of carbonaceous reductant
≤ 950 DEG C of low-temperature reduction conversion, the reduction converted product such as fixation, obtained zinc sulphide and metallic antimony of sulphur can be realized well
Separation can be realized by existing gravity treatment and floatation process.
The method that the sulfide thing of the present invention mutually reduces conversion-beneficiating method processing stibnite concentrate also includes following preferred side
In case.
It is preferably 700~950 DEG C to reduce conversion temperature in preferable scheme.Antimony trisulfide is more beneficial under the temperature conditionss
Occurring the solid sulphur heterogeneous reaction of reduction with zinc oxide and carbonaceous reductant, metallic antimony and zinc sulphide are respectively liquid and solid-state, and two
Carbonoxide and CO gas discharge.
It is 0.5~5h to reduce transformation time in preferable scheme.
Secondary zinc oxide is as sulphur-fixing agent in preferable scheme, with Sb in stibnite concentrate2S3With change into Sb and FeS2Conversion
Mole into secondary zinc oxide needed for FeS is measured for theoretical amount, and the dosage of secondary zinc oxide is the 90~120% of theoretical amount.
The secondary zinc oxide used in preferable scheme for fluorine and the high secondary zinc oxide of chlorinity, wherein Zn >=70%, Pb≤
2%, i.e., using the low-grade secondary zinc oxide cigarette ash of by-product in steel and nonferrous metallurgy, in conversion process is reduced, fluorine and
Chlorine is removed in passing, then is converted into high-quality zinc sulfide concentrates by flotation, low-quality secondary zinc oxide；Traditionally, secondary oxygen
Changing zinc must can be as zinc hydrometallurgy raw material by multiple hearth furnace or rotary kiln vaporization at high temperature or after by the use of neutralizing treatment removing fluorine and chlorine.
Carbonaceous reductant is coal dust and/or coke powder in preferable scheme.
More preferably the dosage of carbonaceous reductant is the 5~20% of stibnite concentrate quality in scheme.
Reduction conversion reaction is realized in multiple hearth furnace or rotary kiln in preferable scheme.Preferably multiple hearth furnace or revolution of the invention
Kiln is easily achieved the continuous operation and large-scale production of technique.
Metallic antimony and zinc sulphide the reduction converted product obtained in technical solution of the present invention is carried by carrying out gravity treatment after crushing
Metallic antimony is taken, gravity tailings carries out flotation output zinc sulfide concentrates.Gravity treatment and flotation are classical ore-dressing techniques, can be used for reference similar
The gravity treatment of material and flotation experience and technical data.
The chemical reaction carried out in technical scheme：
Under the reaction temperature of the present invention, particularly when temperature is in the range of 750 DEG C~950 DEG C, the Sb in raw material2S3And
Following react mainly occurs for ZnO and carbonaceous reductant in auxiliary material：
Sb2S3(l)+3ZnO (s)+3C (s)=2Sb (l)+3ZnS (s)+3CO (g) (1)
Sb2S3(l)+3ZnO (s)+3/2C (s)=2Sb (l)+3ZnS (s)+3/2CO2(g) (2)
Liquid antimony trisulfide thing is mutually converted into liquid metal antimony and solid-state sulphur by solid oxide zinc and charcoal in above-mentioned course of reaction
Change zinc, while release carbon oxide gas.
In addition, the sulphur that part pyrite phase decomposition separates out also reacts generation zinc sulphide with zinc oxide：
FeS2(s)+ZnO (s)+C (s)=FeS (s)+ZnS (s)+CO (g) (3)
FeS2(s)+ZnO (s)+1/2C (s)=FeS (s)+ZnS (s)+1/2CO2(g) (4)
Compared with the prior art, beneficial effects of the present invention：The present invention is first with the high-fluorine chlorine inferior of industrial by-product time oxidation
Zinc cigarette ash carries out reduction conversion and the de- fluorine and chlorine removal of volatilization of stibnite concentrate as solid sulphur reagent, obtains metallic antimony and sulphur
Change zinc reduction converted product.The technique of the present invention belongs to clean environment firendly, low-carbon, low energy consumption type stibium smelting technology, be characterized in it is aobvious and
It is clear to, it is not necessary to which fused salt, reaction temperature is low, and process operation is simple, and reduction converting apparatus can be used in existing process and commonly used
Continuously-running large scale equipment, can meet large-scale industrial production requirement.
Brief description of the drawings
【Fig. 1】The technological process of conversion-beneficiating method is mutually reduced for the thing of present invention processing stibnite concentrate.
Embodiment
Following examples are intended to further illustrate present invention, rather than the model of limitation the claims in the present invention protection
Enclose.
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、SiO27.14、Al2O32.26、CaO0.079、Au 56.6g/t；Sulphur-fixing agent
The composition (wt.%) of secondary zinc oxide is：Zn74.06, Fe0.076, As0.84, Cu0.011, Pb0.81, F0.44, Cl0.38,
SiO20.5、CaO0.016；Reduction coal dust chemical constituent (wt.%) be：C82.33、S3.01、SiO26.66、CaO0.83、
Al2O34.81、MgO0.23.The stibnite concentrate 100g, zinc oxide fume dust 65g, coal dust 6g of mentioned component are weighed respectively, and mixing is equal
It is fitted into after even in graphite crucible, is put into electric furnace the reduction inversion of phases 2.0h at 850 DEG C, inversion of phases product 154g is obtained after cooling,
Its main chemical compositions (wt.%) is：Sb24.16、Fe8.62、S19.87、Zn31.26、Pb0.35、F0.013、Cl0.029.
The removal efficiency of fluorine and chlorine is respectively 93% and 80%.XRD and material phase analysis explanation, antimony thing are mainly mutually metallic antimony, account for total antimony
95.46%, zinc is mainly mutually ZnS and FeS with the thing of iron, accounts for the 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、
SiO221.31、Pb0.01、As0.02、CaO1.52、Al2O30.40、Au0.40g/t。
The stibnite concentrate 100g of mentioned component and secondary zinc oxide cigarette ash 65g, the coal dust 8g of embodiment 1 are weighed, mixing is equal
It is fitted into after even in graphite crucible, is put into electric furnace at 875 DEG C and reacts 1.0h, inversion of phases product 153g is obtained after cooling, its is main
Chemical composition (wt.%) is：Sb36.31、S14.71、Zn31.46、Pb0.34、F0.0093、Cl0.019.The removing of fluorine and chlorine
Rate is respectively 95% and 88%.XRD and material phase analysis explanation, antimony thing are mainly mutually metallic antimony, account for total antimony 96.35%, zinc
Thing is mainly mutually ZnS, accounts for the 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、
SiO216.94、Pb0.085、Zn0.018、As0.02、CaO0.69、Al2O32.16、Au0.31g/t。
The stibnite concentrate 100g of mentioned component and secondary zinc oxide cigarette ash 60g, the coal dust 10g of embodiment 1 are weighed, mixing is equal
It is fitted into after even in graphite crucible, is put into electric furnace at 900 DEG C and reacts 45min, inversion of phases product 148g is obtained after cooling, its is main
Chemical composition (wt.%) is：Sb32.53、S14.74、Zn30.00、Fe1.66、Pb0.38、F0.0054、Cl0.012.Fluorine and chlorine
Removal efficiency be respectively 97% and 92%.XRD and material phase analysis explanation, antimony thing are mainly mutually metallic antimony, account for total antimony
97.25%th, the thing of zinc is mainly mutually ZnS, accounts for the 95.32% of total zinc amount.
Claims (4)
1. a kind of method that sulfide thing mutually reduces conversion-beneficiating method processing stibnite concentrate, it is characterised in that by antimony trisulfide essence
Ore deposit and secondary zinc oxide carry out reduction 0.5~5h of conversion at a temperature of 700~950 DEG C, generate metal in the presence of carbonaceous reductant
Antimony and zinc sulphide reduction converted product, reduction converted product isolate metallic antimony and zinc sulphide essence by gravity treatment combination floatation process
Ore deposit；Described secondary zinc oxide is high-fluorine chlorine secondary zinc oxide, wherein Zn >=70%, Pb≤2%；Described reduction conversion reaction is more
Realized in thorax stove or rotary kiln.
2. according to the method for claim 1, it is characterised in that described secondary zinc oxide is as sulphur-fixing agent, with antimony trisulfide essence
Sb in ore deposit2S3It is fully converted into Sb and FeS2The amount for being fully converted into secondary zinc oxide needed for FeS is measured for theoretical amount, secondary zinc oxide
Dosage be theoretical amount 90~120%.
3. according to the method for claim 1, it is characterised in that described carbonaceous reductant is coal dust and/or coke powder.
4. the method according to claim 1 or 3, it is characterised in that the dosage of described carbonaceous reductant is antimony trisulfide essence
The 5~20% of mineral amount.
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| 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 |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4333762A (en) * | 1980-03-20 | 1982-06-08 | Asarco Incorporated | Low temperature, non-SO2 polluting, kettle process for the separation of antimony values from material containing sulfo-antimony compounds of copper |
| CN101914693A (en) * | 2010-09-01 | 2010-12-15 | 中南大学 | Clean metallurgical method for low-temperature molten salt of antimony |
| CN102433448A (en) * | 2011-12-28 | 2012-05-02 | 北京矿冶研究总院 | Smelting method of antimony-zinc-lead-containing concentrate |
| CN102965510A (en) * | 2012-11-27 | 2013-03-13 | 中南大学 | Reduction sulfur-fixing bath smelting method and device of low-sulfur lead-containing secondary material and iron-rich heavy metal solid waste |
| 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
- 2015-06-30 CN CN201510385266.7A patent/CN104975166B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4333762A (en) * | 1980-03-20 | 1982-06-08 | Asarco Incorporated | Low temperature, non-SO2 polluting, kettle process for the separation of antimony values from material containing sulfo-antimony compounds of copper |
| CN101914693A (en) * | 2010-09-01 | 2010-12-15 | 中南大学 | Clean metallurgical method for low-temperature molten salt of antimony |
| CN102433448A (en) * | 2011-12-28 | 2012-05-02 | 北京矿冶研究总院 | Smelting method of antimony-zinc-lead-containing concentrate |
| CN102965510A (en) * | 2012-11-27 | 2013-03-13 | 中南大学 | Reduction sulfur-fixing bath smelting method and device of low-sulfur lead-containing secondary material and iron-rich heavy metal solid waste |
| 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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