CN104120266A - Method for preparing high-quality anti-position indium feed liquid by using complex indium copper enrichment residues - Google Patents
Method for preparing high-quality anti-position indium feed liquid by using complex indium copper enrichment residues Download PDFInfo
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- CN104120266A CN104120266A CN201410376196.4A CN201410376196A CN104120266A CN 104120266 A CN104120266 A CN 104120266A CN 201410376196 A CN201410376196 A CN 201410376196A CN 104120266 A CN104120266 A CN 104120266A
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Abstract
The invention discloses a method for preparing a high-quality anti-position indium feed liquid by using complex indium copper enrichment residues. The method comprises the following steps: washing indium copper enrichment residues in a weak acid, performing open leaching on arsenic, iron, tin, lead, zinc, antimony, bismuth, silicon and thallium in the residues in an indium system, remaining indium and copper in the residues, and performing liquid-solid separation to obtain the filter residues; leaching the filter residues by using concentrated sulfuric acid, and performing liquid-solid separation to obtain copper residues and filtrate; performing extraction and reverse extraction on the filtrate to obtain an anti-position indium liquid; and converting the anti-position indium liquid by using coarse indium, performing displacement precipitation on impurity ions such as arsenic, iron, tin, lead, zinc, antimony, bismuth, silicon and thallium to enter the residues, and performing liquid-solid separation to obtain the qualified anti-position indium feed liquid in which the impurities are removed. Impurity elements in the complex indium copper enrichment residues are leached through open weak acid leaching, the impurity removal pressure of subsequent operation is reduced, the indium recovery rate is ensured, most of the impurities in the anti-position indium liquid by using coarse indium are replaced by using the coarse indium, the impurity removal effect is obvious, the antimony impurity content is reduced by over 100 times at a time, and the indium ion concentration of the anti-position indium feed liquid is improved. The method is convenient and feasible, novel equipment is not needed, and high-quality indium ingots can be produced when a main production process is not transformed.
Description
Technical field
The present invention relates to hydrometallurgical technology, specifically the complicated indium copper of a kind of use enrichment slag is prepared the method for the anti-indium feed liquid of high-quality.
Background technology
Anti-solution of indium is exactly the solution of indium that contains of stripping and obtaining, and is the raw material of indium metal electrolysis.
Before 2011, what the quality standard of rare precious metal indium was carried out is the standard of YS/T257-1998, the trade mark is In99993, after 2011, its quality standard changes to YS/T257-2009, the trade mark is In99995, the key distinction of two standards is that the content requirement that is lead, zinc, copper, iron, tin, cadmium, aluminium, arsenic, thallium to 9 large impurity in indium ingot all increases, and the difficulty in production technique is increasing.
And on the other hand, along with the exploitation of high-quality zinc ore concentrate and the continuous increase of buying difficulty, high quality raw material source is limited, manufacturing enterprise is for maintaining normal production, have to accept the zinc ore concentrate raw material of all kinds of complicated components, so various impurity elements enter in production system through various channels, associated metal indium is wherein after Rotary Kiln volatilizing and enriching, and a large amount of impurity also enters in indium production system in the lump.Taking applicant unit as example, should ground environmental administration requirement, must be to Rotary Kiln tail gas, relieving haperacidity tail gas is administered, adopting oxide powder and zinc to do after absorption agent, arsenic, antimony, fluorine, chlorine, silicon, impurity in the flue gases such as thallium all enters in indium production system, antimony in reversal indium liquid constantly raises, after zine plate displacement, the sponge indium of output has occurred pressing not agglomerating, the phenomenons such as sponge indium blackout, electrolysis is simultaneously separated out indium thallium content and is also constantly risen, increase cost and difficulty to the refining removal of impurities of separating out indium, the indium ingot difficult quality of once electrolytic output reaches the requirement of above-mentioned standard.
Although antimony is not the impurity element of subscript industry standard control, as mentioned above, due to the existence of antimony, cause the sponge indium of the rear output of zine plate displacement to occur that pressure is not agglomerating, the phenomenons such as sponge indium blackout, have increased difficulty to subsequent job, and cost increases.Do not have ready-made prior art to use for reference and how to remove impurity antimony.Therefore, the technology of high-test metal indium is extracted in research and development taking complicated indium copper enrichment slag as raw material, particularly how to remove wherein reversal indium liquid high efficiency, low cost and comprise that antimony is at interior impurity component, has Great significance for subsequent handling provides qualified feed liquid.
Summary of the invention
Object of the present invention is exactly to propose for the problems referred to above the method that the complicated indium copper of a kind of use enrichment slag is prepared the anti-indium feed liquid of high-quality, the method can be removed complicated indium copper enrichment slag high efficiency, low cost and be comprised that antimony is at interior impurity component, output meets the anti-indium feed liquid of indium metal subsequent technique requirement, guarantees the quality product of high purity indium.
Object of the present invention realizes by following means:
The complicated indium copper of use enrichment slag is prepared a method for the anti-indium feed liquid of high-quality, it is characterized in that it has the following steps:
(1), indium copper enrichment slag washs in weak acid, and the arsenic in this slag, iron, tin, lead, zinc, antimony, bismuth, silicon, thallium open circuit are leached to indium system, indium and copper are stayed in slag, the liquid-solid filter residue that separates to obtain;
(2) with the vitriol oil, filter residue is leached, liquid-solidly separate to obtain copper ashes and filtrate;
(3) filtrate of step (2) obtains reversal indium liquid after extraction and back-extraction;
(4) with thick indium conversion reversal indium liquid, the foreign ion cementations such as arsenic wherein, iron, tin, lead, zinc, antimony, bismuth, silicon, thallium are entered in slag, liquid-solid separation obtains reversal indium liquid after qualified removal of impurities.
Whole acid concentration in step (1) is 0.5～10g/l.
Step (2) gained copper ashes send copper recovery process to reclaim copper.
The extraction gained raffinate of step (3) send Zn system recycling.
Between the extraction and back-extraction of step (3), have the pickling operation of pair load organic phases to connect, pickling gained pickle solution send indium leaching system use again, and the load organic phases after pickling is entered back extraction operation.
The thick indium displacement processing temperature of step (4) is in 45～60 DEG C.
The thick indium displacement operation of step (4), the thick indium amount once dropping into the as required amount of substitutional impurity determines.
The liquid-solid separation of step (4) adopts two-stage filtration, i.e. the mode that pressure filter press filtration+accurate filter filters reduces the solid content of reversal indium liquid after removal of impurities to greatest extent, and after filtering, solution is limpid transparent.
After step (4) gained removal of impurities, reversal indium liquid obtains final high purity indium product through zine plate displacement, alkali fusion, electrolysis and refining.
Feature of the present invention is:
1, first complicated indium copper enrichment slag is leached to a part of impurity with open circuit mode weak acid, in alleviating subsequent job removal of impurities pressure, guarantee that most indiums and copper enter in slag, ensure indium recovery;
2, effectively removed the greatly once impurity in solution with thick indium positive plate displacement reversal indium liquid, the particularly wherein disposable reduction of antimony foreign matter content more than 100 times, all the other foreign matter contents do not reduce by 2～20 times not etc., and impurity-eliminating effect is fairly obvious.Increase substantially again reversal indium liquid indium ion concentration, be conducive to carrying out smoothly of follow-up indium-extracting process simultaneously;
3, the present invention is convenient and easy, and without increasing new installation, for enterprise, main body production technique does not carry out, in the situation of large transformation, by process control and optimization, can producing the indium ingot of high-quality yet.
Brief description of the drawings
Accompanying drawing is process flow sheet of the present invention.
Embodiment
Example 1
The a collection of indium copper enrichment slag obtaining through rotary kiln processing, containing impurity such as a large amount of arsenic, iron, tin, lead, zinc, antimony, bismuth, silicon, thalliums, these impurity are present in slag with variform, according to above-mentioned technique, first to it with the weak acid washing of opening a way, so that these impurity elements are leached and enter solution.Weak acid is zinc electrolysis waste solution, and acidity control when operation terminal is leached in washing is at 0.5～10g/l.Washing is rear with how filter carries out liquid-solid separation, soak and after slag washs again, enter peracid agricultural and leach, to indium is immersed in solution, due to the limitation of weak acid, above-mentioned impurity element can not thoroughly be deviate from the time that weak acid washs, and when high Ore Leaching, inevitably immerses in solution with indium simultaneously.Only the copper soaking in distress is stayed in slag, after liquid-solid separation, becomes copper ashes, send copper recovery process to extract copper.
The conventional extraction and back-extraction access method of high acid leaching liquor utilization is processed, and technological process as shown in drawings, get between operation and establish one pickling operation by extraction and back-extraction, and the load organic phases after pickling obtains reversal indium liquid after dilute hydrochloric acid back extraction.Reversal indium liquid assay is learnt to above-mentioned impurity component still exists in a large number, specific as follows:
As
3+：0.5g/l、Sn
4+：0.15?g/l、Sb
2+：2.45g/l、Bi
2+：0.085g/l、Pb
2+：0.01g/l，Tl
2+:0.005?g/l。
Such reversal indium liquid does not obviously meet the follow-up requirement of proposing indium operation, must further process, can to remove to greatest extent impurity.So, the positive plate that adds thick indium to make in reversal indium liquid, temperature is controlled at 60 DEG C of left and right, and the indium metal generation replacement(metathesis)reaction in all kinds of impurity and positive plate forms precipitation, sinks to bottom land, and after removal of impurities, the foreign matter content of reversal indium liquid significantly reduces, and result of laboratory test is: As
3+: 0.024g/l, Sn
4+: 0.016 g/l, Sb
2+: 0.022g/l, Bi
2+: trace, Pb
2+: 0.009g/l, Tl
2+: 0.002 g/l.
Variation from the each foreign matter content in thick indium displacement front and back: antimony ion concentration has wherein reduced by 110 times, and trivalent arsenic ion has reduced nearly 20 times, and tetravalent tin ion has reduced by 8 times, and two valency bismuth ions are almost reduced to zero (trace), and two valency thallium ions have reduced by 1.5 times.Reversal indium liquid has obtained very big purification.
After removal of impurities, reversal indium liquid adopts accurate filter to filter, realize liquid-solid separation, clean reversal indium liquid after clarification is clear thorough bright, then replaces with zine plate, output high-quality sponge indium, it is not agglomerating that sponge indium no longer includes aforementioned pressure while pressing group, the phenomenons such as sponge indium blackout, and electrolysis operation is also smooth and easy, applicant unit is not because raw material sources change greatly, and increase new equipment, and but overcome technical barrier by method of the present invention, ensure that the trade mark is that the quality of In99995 high purity indium is all up to standard.
Example 2
Another batch of indium copper enrichment slag that source is complicated, after the method weak acid open circuit leaching identical with upper example, high Ore Leaching, extraction, pickling and back extraction, gained reversal indium liquid is as follows containing assorted situation:
As
3+：0.38g/l、Sn
4+：0.11?g/l、Sb
2+：1.76g/l、Bi
2+：0.13g/l、Pb
2+：0.014g/l，Tl
2+:0.006?g/l。
After thick indium replacement Treatment, after gained removal of impurities, reversal indium liquid is as follows containing assorted index:
As
3+: 0.004g/l, Sn
4+: 0.009g/l, Sb
2+: 0.031g/l, Bi
2+: trace, Pb
2+: 0.007g/l, Tl
2+: 0.0015g/l.
Example 3
Another batch of indium copper enrichment slag that source is complicated, after the method weak acid open circuit leaching identical with upper example, high Ore Leaching, extraction, pickling and back extraction, gained reversal indium liquid is as follows containing assorted situation:
As
3+：1.2g/l、Sn
4+：0.25?g/l、Sb
2+：3.5g/l、Bi
2+：0.3g/l、Pb
2+：0.05g/l，Tl
2+:0.02g/l。
After thick indium replacement Treatment, after gained removal of impurities, reversal indium liquid is as follows containing assorted index:
As
3+: 0.08g/l, Sn
4+: 0.021g/l, Sb
2+: 0.048g/l, Bi
2+: trace, Pb
2+: 0.004g/l, Tl
2+: 0.001g/l.
Claims (9)
1. a method of preparing the anti-indium feed liquid of high-quality with complicated indium copper enrichment slag, is characterized in that it has the following steps:
(1), indium copper enrichment slag washs in weak acid, and the arsenic in this slag, iron, tin, lead, zinc, antimony, bismuth, silicon, thallium open circuit are leached to indium system, indium and copper are stayed in slag, the liquid-solid filter residue that separates to obtain;
(2) with the vitriol oil, filter residue is leached, liquid-solidly separate to obtain copper ashes and filtrate;
(3) filtrate of step (2) obtains reversal indium liquid after extraction and back-extraction;
(4) with thick indium conversion reversal indium liquid, the foreign ion cementations such as arsenic wherein, iron, tin, lead, zinc, antimony, bismuth, silicon, thallium are entered in slag, liquid-solid separation obtains reversal indium liquid after qualified removal of impurities.
2. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that the whole acid concentration in step (1) is 0.5～10g/l.
3. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that step (2) gained copper ashes send copper recovery process to reclaim copper.
4. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that the extraction gained raffinate of step (3) send Zn system recycling.
5. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that having between the extraction and back-extraction of step (3) the pickling operation of pair load organic phases to connect, pickling gained pickle solution send indium leaching system use again, and the load organic phases after pickling is entered back extraction operation.
6. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that the thick indium displacement processing temperature of step (4) is 45～60 DEG C.
7. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that the thick indium displacement operation of step (4), and the thick indium amount once dropping into the as required amount of substitutional impurity determines.
8. prepare the method for the anti-indium feed liquid of high-quality according to the complicated indium copper of the use described in claim 1 or 7 enrichment slag, the liquid-solid separation that it is characterized in that step (4) adopts two-stage filtration, it is the mode that pressure filter press filtration+accurate filter filters, reduce to greatest extent the solid content of reversal indium liquid after removal of impurities, after filtering, solution is limpid transparent.
9. the complicated indium copper of use according to claim 1 enrichment slag is prepared the method for the anti-indium feed liquid of high-quality, it is characterized in that step (4) gained removal of impurities after reversal indium liquid obtain final high purity indium product through zine plate displacement, alkali fusion, electrolysis and refining.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105219970A (en) * | 2015-10-29 | 2016-01-06 | 红河锌联科技发展有限公司 | A kind ofly roast in dirt the method reclaiming many metals and calcium chloride |
| CN105483377A (en) * | 2015-12-16 | 2016-04-13 | 株洲冶炼集团股份有限公司 | Method for refining indium reverse extraction liquid and gathering valuable metal and application |
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Cited By (3)
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|---|---|---|---|---|
| CN105219970A (en) * | 2015-10-29 | 2016-01-06 | 红河锌联科技发展有限公司 | A kind ofly roast in dirt the method reclaiming many metals and calcium chloride |
| CN105219970B (en) * | 2015-10-29 | 2017-07-07 | 红河锌联科技发展有限公司 | A kind of method that many metals and calcium chloride are reclaimed in roasting dirt |
| CN105483377A (en) * | 2015-12-16 | 2016-04-13 | 株洲冶炼集团股份有限公司 | Method for refining indium reverse extraction liquid and gathering valuable metal and application |
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