CN101816979B - Flotation activating agent of marmatite and blende and preparation method thereof - Google Patents

Flotation activating agent of marmatite and blende and preparation method thereof Download PDF

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Publication number
CN101816979B
CN101816979B CN201010124710.7A CN201010124710A CN101816979B CN 101816979 B CN101816979 B CN 101816979B CN 201010124710 A CN201010124710 A CN 201010124710A CN 101816979 B CN101816979 B CN 101816979B
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solution
marmatite
activating agent
ore
quality
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CN101816979A (en
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童雄
谢贤
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention provides a flotation activating agent of marmatite and blende, which is a coordination compound of copper and ammonia and is characterized in that the molecular formula of the coordination compound is [Cu(NH3)x]2+, wherein X=1-8. The activating agent of the invention solves the problem of selected activation and inhibition of marmatite, overcomes the problems of low activation selection, low zinc concentrate grade, serious metal mutual containing and the like of common activating agent copper sulphate and solves the problems of high-efficiency enrichment and comprehensive recovery of concomitant rare and noble metal. The activating agent is activated under the condition that pH value is as low as 7-11, provides necessary guarantee for reducing lime dosage in production, reasonably and effectively recovers other sulfide minerals and comprehensively recovers rare metal, and has the advantages of high activation efficiency, low production cost and the like. The invention also applies a preparation method for the flotation activating agent.

Description

Flotation activating of marmatite and zincblende and preparation method thereof
Technical field
The present invention relates to ore dressing engineering and rare precious metal comprehensive utilization technique field, particularly a kind of efficient activator for marmatite and Sphalerite flotation and its production and use.
Background technology
China's zinc metal reserves account for 15% of world's gross reserves, occupy the second in the world, and simultaneously China is also a zinc big producing country, and zinc metal output reached 374.9 ten thousand tons in 2007, ranked first in the world, and export volume reaches 27.56 ten thousand tons.development along with national economy, increase to zinc metal demand, in the urgent need to the resource of complicated difficult choosing is developed and is utilized, it is more domestic that leaded, zinc, sulphur, iron or zinc, copper, tin, iron, the plumbous zinc ore mountain of sulphur and zinc-tin mine etc. be in various degree the marmatite that contains choosing in distress all, for example, the large factory in Guangxi, the plumbous zinc ore in river three, the yellow sand level ground in Hunan, Pan Jiachong, the plumbous zinc ore of HERBA ONYCHII, the plumbous zinc ore in the Hezhang in Guizhou, the plumbous zinc ore in tin iron mountain in Qinghai, the plumbous zinc ore in the XiLin in Heilungkiang, the Fangniugou Pyrite in Jilin, therefore ox is washed in a pan plumbous zinc ore, the plumbous zinc ore of thick mother-in-law's col in Guangdong, all Long Xinxikuang and the lead ore of Lancang etc. in Yunnan.The marmatite iron content in these mines is generally 8-12%, have up to 26%, therefore, adopt suitable marmatite ore-dressing technique, marmatite is developed and utilized significant.
Zincblende, marmatite and wurtzite are three kinds of common zinc sulfide minerals.Zincblende (ZnS) belongs to isometric system, and crystalline form is often tetrahedron; Natural cleiophane contains zinc 67.1%, 32.9% sulphur.Wurtzite is general similar to the physical property of zincblende, generally rare in practice.The zincblende of iron content more than 6% is called marmatite [(Zn XFe 1-XS)], zinc blend lattice is often sneaked into isomorph by Tie Tong, and the quantity of infiltrating iron is generally 6~12% (Gao Shida 26%).
In actual process, marmatite than zincblende show not easily-activated, floatability is poor, to characteristics such as medium sensitivities, it is more difficult to separate with mineral such as magnetic iron ore, pyrite and mispickel.Simultaneously, compare with other sulfide mineral, the floatability of marmatite or zincblende is far smaller than other sulfide minerals, general not activated marmatite or the flotation of zincblende need to need the above xanthate of 4 carbon with hybrid collector or chain length, make the flotation of zincblende seem more difficult.Therefore, activation is the important step in the marmatite ore dressing.Main with the activator of copper sulphate as marmatite in producing at present, however copper sulphate has following defective as activator:
(1) select marmatite for difficulty, the activation of copper sulphate is unsatisfactory, does not reach good index.
(2) activity function of copper sulphate strengthens along with the enhancing of alkalescence, therefore, the activation of copper sulphate is generally to carry out under a high-alkali environment, thereby certainly will add a large amount of lime aborning, so just suppress the flotation of the relatively poor zincblende of floatability, marmatite and oxidized mineral such as chalcopyrite.
(3) rolling up of lime consumption not only increases beneficiation cost, increases workman's workload, and from ore dressing and comprehensive the recovery and the angle of utilizing, the lime of large consumption is also worthless.After adjusting the pH value and suppress other sulfide minerals with a large amount of lime in selecting the zinc process, during next step flotation must come with a large amount of sulfuric acid and the lime in ore pulp, to reduce the pH value, perhaps add a large amount of activator activation and other sulfide minerals of flotation, this has not only further increased beneficiation cost, and the calcium sulfate that lime and sulfuric acid reaction generate is easy to blocking pipe, at the gravitational separation equipment surface scale, seriously affects the continuity of mineral processing circuit and the rate of recovery of gravity treatment; In addition, sulfuric acid also can produce etching problem to pipeline and preparation equipment.
(4) copper sulphate and combination activator thereof in the activation marmatite, also can activate difficult floating magnetic iron ore, increase the iron content in zinc concentrate, to follow-up hydrometallurgy process, zinc and indium further separated with enrichment very unfavorable.In order to suppress magnetic iron ore, the kind of inhibitor may many and large usage quantity, and flow process is also more complicated.If the activator that adopts is under low alkali condition, do not activate magnetic iron ore or pyrite and only activate marmatite and zincblende, can simplify the deironing sulfur removal technology, save production cost, improve grade and the rate of recovery of zinc concentrate zinc, indium, silver etc., reduce the content of iron and sulphur in zinc concentrate, reduce the element such as iron in zinc concentrate to the adverse effect of follow-up metallurgical process; Simultaneously, can also improve significantly the rate of recovery of reselection operation.
As seen, there are a lot of defectives in the conventional activator of the at present domestic and international marmatite that adopts and inhibitor, and its activation and the efficient that suppresses and selectively not high cause the rate of recovery of zinc and zinc concentrate grade not high, and metal contains seriously mutually.
Summary of the invention
The objective of the invention is: overcome the deficiency of existing activator copper sulphate, the dressing activator of the high marmatite of a kind of activation efficiency and zincblende is provided.This activator has the characteristics such as selective height, the rate of recovery are high, environmental friendliness.Because the pH value of needs is lower, the scope of application is wider.
Technical scheme of the present invention is: the dressing activator of making marmatite and zincblende with the complex of copper and ammonia is.Activator of the present invention can use under the low alkalinity environmental condition, according to the concrete condition of ore, is to use under 7~11 environment in the pH value, and is respond well.
The flotation activating of marmatite of the present invention and zincblende is the complex of copper and ammonia, it is characterized in that, the molecular formula of said complex is: [Cu (NH 3) x] 2+, X=1 in formula~8.
The preparation method of the flotation activating of marmatite of the present invention and zincblende, it is characterized in that, preparation section is as follows, said in the operation of following a~c " by the suitable metered proportions of chemical reaction " refers to the completeness in order to react, the additional proportion of central ion, ligand must satisfy the corresponding conditions of chemical reaction at least, under the principle of not wasting, excessive 0.5~10.0 quality % of the comparable central ion of ligand;
A, by the suitable metered proportions of chemical reaction, ammonia is dissolved in a kind of solvent of selecting from the second alcohol and water, obtains the first solution (A), the concentration of solution is 0.5~25 quality %;
B, press the suitable metered proportions of chemical reaction with Cu (NO 3) 23H 2O or CuSO 45H 2O is dissolved in a kind of solvent of selecting from the second alcohol and water, obtains the second solution (B), and the concentration of solution is 0.5~50 quality %;
C, press the suitable metered proportions of chemical reaction with NaOH and Na 2CO 3Be dissolved in a kind of solvent of selecting from the second alcohol and water, obtain the third solution (C), the concentration of solution is 5~40 quality %;
Under d, stirring, A solution is gently joined in B solution, under the mixing speed of 150~200 rev/mins, reacted under room temperature 2~30 minutes, add again C solution, continue reaction 3~25 minutes under room temperature, add at last a kind of solution of selecting from the second alcohol and water, reaction generates the crude product of solids of sedimentation;
E, reacted solution decompression is filtered, use C 2H 5The sediment that the OH washing and filtering obtains blots with filter paper, then at air drying, namely obtains the flotation activating sterling.
This activator can adopt common copper to coordinate technique to be prepared with ammonia etc., in the ore dressing process in the plumbous zinc ore that contains marmatite and zincblende and zinc-tin ore deposit, as activator, the marmatite in ore and zincblende are activated, improve the floatability of marmatite and zincblende.In complex, the ratio of copper and ammonia etc. can be according to the situation of concrete ore dressing raw material, uses in lower pH value scope and certain consumption, need to not operate under high alkali environment.
This activator all can use in the flotation of marmatite and zincblende polymetallic ore and gravity separation technology.
The present invention adopts the complex of copper and ammonia etc. as activator, effect due to copper and ammonia etc., strengthened the hydrophobicity of surface of marmatite, make this activator only optionally activate marmatite, overcome conventional activator selectively not high, the zinc concentrate grade is not high and reclaim zinc and indium etc. for follow-up metallurgical process and cause disadvantageous technical bottleneck, has solved well the problem of marmatite floatation process activation efficiency.
Compare with prior art, the present invention has the following advantages or good effect:
1, solved a difficult difficult problem of selecting the marmatite activation;
2, activator of the present invention need to not activate under high pH value condition, mainly uses under neutrality, low alkalinity environment, and the ore pulp environment pH value of using is 7~11.This just provides necessary assurance for reducing lime consumption, reasonable effectively recovery other sulfide minerals, cassiterite in producing and comprehensively reclaiming rare precious metal.
3, the production cost of activator is lower than the cost of copper sulphate, be also that enterprise is under low basicity condition, realize efficient separation and the enrichment of zinc-sulphur, tin-sulphur, lead-zinc etc., and can create condition for carrying out effective desulfurization, reduction sulfuric acid consumption, raising zinc indium grade and the rate of recovery before reselection operation.
The specific embodiment:
The present invention is further elaborated below in conjunction with embodiment.
Embodiment 1
Get appropriate ammonia and be dissolved in ethanol, obtain the first solution (A), the concentration of solution is 0.5 quality %; Get appropriate Cu (NO 3) 23H 2O is dissolved in ethanol, obtains the second solution (B), and the concentration of solution is 0.5 quality %; Press the suitable metered proportions of chemical reaction with NaOH and Na 2CO 3Be dissolved in ethanol, obtain the third solution (C), the concentration of solution is 5 quality %; Under stirring, A solution is gently joined in B solution, under the mixing speed of 150 rev/mins, under room temperature, reaction is 2 minutes, then adds C solution, continues reaction 3 minutes under room temperature, adds at last entry, and reaction generates the crude product of solids of sedimentation; Reacted solution decompression is filtered, use C 2H 5The sediment that the OH washing and filtering obtains blots with filter paper, then at air drying, namely obtains the flotation activating sterling, is the Novel mineral activator of marmatite and zincblende.
Treat that ore dressing is the ore of Dachang, Guangxi, the elements such as leaded in ore, antimony, zinc, sulphur, iron, indium and silver, wherein mineral content contains 0.7~10.5% marmatite and 0.4% above zincblende, and in marmatite, the content of iron reaches 11% left and right.Adopt common ore-dressing technique, add this activator in floatation process, add common collecting agent, through conventional flotation, ore dressing environment pH value is 7.
Adopt this activator, through above-mentioned technical process, can reclaim well marmatite and zincblende.
Embodiment 2
Get appropriate ammonia and be dissolved in the water, obtain the first solution (A), the concentration of solution is 6.25 quality %; Get appropriate CuSO 45H 2O is dissolved in the water, and obtains the second solution (B), and the concentration of solution is 25 quality %; Press the suitable metered proportions of chemical reaction with NaOH and Na 2CO 3Be dissolved in the water, obtain the third solution (C), the concentration of solution is 20 quality %; Under stirring, A solution is gently joined in B solution, under the mixing speed of 200 rev/mins, under room temperature, reaction is 15 minutes, then adds C solution, continues reaction 10 minutes under room temperature, adds at last ethanol, and reaction generates the crude product of solids of sedimentation; Reacted solution decompression is filtered, use C 2H 5The sediment that the OH washing and filtering obtains blots with filter paper, then at air drying, namely obtains the flotation activating sterling, is the Novel mineral activator of marmatite and zincblende.
Treat that ore dressing is ore in imperial zinc-tin mining area all, wherein contain zinc, copper, tin, iron, sulphur, indium, gallium, germanium, gold and the element such as silver-colored, wherein mineral content contains 0.7~11.8% marmatite and 0.5% above zincblende, and in marmatite, the content of iron reaches more than 20%.Adopt common ore-dressing technique, add this activator in floatation process, then add common collecting agent, through conventional flotation, ore dressing environment pH value is 9.
Adopt this activator, through above-mentioned technical process, sub-elect marmatite and the 50% above zincblende of grade more than 46%, the rate of recovery can reach more than 90% respectively.
Embodiment 3
Get appropriate ammonia and be dissolved in the water, obtain the first solution (A), the concentration of solution is 25 quality %; Get appropriate Cu (NO 3) 2Be dissolved in the water, obtain the second solution (B), the concentration of solution is 50 quality %; Press the suitable metered proportions of chemical reaction with NaOH and Na 2CO 3Be dissolved in the water, obtain the third solution (C), the concentration of solution is 40 quality %; Under stirring, A solution is gently joined in B solution, under the mixing speed of 150 rev/mins, under room temperature, reaction is 30 minutes, then adds C solution, continues reaction 25 minutes under room temperature, adds at last ethanol, and reaction generates the crude product of solids of sedimentation; Reacted solution decompression is filtered, use C 2H 5The sediment that the OH washing and filtering obtains blots with filter paper, then at air drying, namely obtains the flotation activating sterling, is the Novel mineral activator of marmatite and zincblende.
Treat that ore dressing is the ore in lead ore of Lancang district, contain zinc, copper, iron, sulphur, indium, gold and the element such as silver-colored in ore, wherein mineral content contains 0.5~9.8% marmatite and 0.6% above zincblende.Adopt common ore-dressing technique, add this activator in floatation process, then add common collecting agent, with the process conventional flotation, ore dressing environment pH value is 11.
Adopt this activator, through above-mentioned technical process, sub-elect marmatite and the 46% above zincblende of grade more than 40%.
Embodiment 4
Get appropriate ammonia and be dissolved in ethanol, obtain the first solution (A), the concentration of solution is 5 quality %; Get appropriate CuSO 45H 2O is dissolved in ethanol, obtains the second solution (B), and the concentration of solution is 40%; Press the suitable metered proportions of chemical reaction with NaOH and Na 2CO 3Be dissolved in ethanol, obtain the third solution (C), the concentration of solution is 10 quality %; Under stirring, A solution is gently joined in B solution, under the mixing speed of 180 rev/mins, under room temperature, reaction is 20 minutes, then adds C solution, continues reaction 15 minutes under room temperature, adds at last entry, and reaction generates the crude product of solids of sedimentation; Reacted solution decompression is filtered, use C 2H 5The sediment that the OH washing and filtering obtains blots with filter paper, then at air drying, namely obtains the flotation activating sterling, is the Novel mineral activator of marmatite and zincblende.
Treat that ore dressing is ore in imperial zinc-tin mining area all, contain zinc, copper, tin, iron, sulphur, indium, gallium, germanium, gold and the element such as silver-colored in ore, wherein mineral content contains 0.7~11.8% marmatite and 0.5% above zincblende.Adopt common ore-dressing technique, add this activator in floatation process, then add common collecting agent, with the process conventional flotation, ore dressing environment pH value is 8.
Adopt this activator, through above-mentioned technical process, sub-elect marmatite and 50% above zincblende more than 45%, the rate of recovery can reach more than 90% respectively.
Comparison by activator of the present invention and copper sulphate, this novel activator has very large advantage, it is not only better to the activation effect of marmatite, and need to not activate under high pH value condition, this is significant aborning, it significantly reduces lime and sulfuric acid consumption in producing, reclaiming efficiently other sulfide minerals, cassiterite and comprehensively reclaiming rare precious metal provides necessary assurance.
The cost of activator of the present invention is lower than copper sulphate, be also that enterprise is under low basicity condition, realize carrying out effective desulfurization before zinc-sulfur highly effective separation and enrichment, reselection operation, reduce the sulfuric acid consumption, improve grade and the rate of recovery of the metals such as zinc and tin, market prospects are fine.

Claims (1)

1. the preparation method of the flotation activating of a marmatite and zincblende, it is characterized in that, preparation section is as follows, said in following 2.1~2.3 operation " by the suitable metered proportions of chemical reaction " refers to the completeness in order to react, the additional proportion of central ion, ligand must satisfy the corresponding conditions of chemical reaction at least, under the principle of not wasting, ligand is than excessive 0.5~10.0 quality % of central ion;
2.1, by the suitable metered proportions of chemical reaction, ammonia is dissolved in a kind of solvent of selecting from the second alcohol and water, obtain the first solution A, the concentration of solution is 0.5~25 quality %;
2.2, press the suitable metered proportions of chemical reaction with Cu (NO 3) 23H 2O or CuSO 45H 2O is dissolved in a kind of solvent of selecting from the second alcohol and water, obtains the second solution B, and the concentration of solution is 0.5~50 quality %;
2.3, press the suitable metered proportions of chemical reaction with NaOH and Na 2CO 3Be dissolved in a kind of solvent of selecting from the second alcohol and water, obtain the third solution C, the concentration of solution is 5~40 quality %;
2.4, the first solution A is gently joined in the second solution B under stirring, mixing speed at 150~200 rev/mins, reacted under room temperature 2~30 minutes, add again the third solution C, continue reaction 3~25 minutes under room temperature, add at last a kind of solution of selecting from the second alcohol and water, reaction generates the crude product of solids of sedimentation;
2.5, reacted solution decompression is filtered, use C 2H 5The sediment that the OH washing and filtering obtains blots with filter paper, then at air drying, namely obtains the flotation activating sterling.
CN201010124710.7A 2010-03-16 2010-03-16 Flotation activating agent of marmatite and blende and preparation method thereof Expired - Fee Related CN101816979B (en)

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CN105772226A (en) * 2016-03-16 2016-07-20 云南缘矿科技开发有限公司 Flotation activating agent for fine-grain cassiterite and preparing method of flotation activating agent
CN108940604B (en) * 2018-07-27 2020-07-21 攀枝花学院 Ferro-sphalerite flotation activator and preparation method and application thereof
CN111659531B (en) * 2020-06-16 2021-03-23 昆明理工大学 Method for flotation separation of lead-zinc sulfide ore containing intergrowth
CN111659529B (en) * 2020-06-16 2021-02-19 昆明理工大学 Method for separating and utilizing micro-fine particle embedded lead-zinc oxide ore by dressing and smelting

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