CN101994009A - Method for enriching and recovering indium from zinc oxide acid supernate - Google Patents
Method for enriching and recovering indium from zinc oxide acid supernate Download PDFInfo
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- CN101994009A CN101994009A CN2010105832788A CN201010583278A CN101994009A CN 101994009 A CN101994009 A CN 101994009A CN 2010105832788 A CN2010105832788 A CN 2010105832788A CN 201010583278 A CN201010583278 A CN 201010583278A CN 101994009 A CN101994009 A CN 101994009A
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- indium
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Abstract
The invention discloses a method for enriching and recovering indium from zinc oxide acid supernate, which is characterized by comprising the following: a step A of reduction and purification, which is to put iron powder into zinc oxide acid supernate to reduce Fe<3+> into Fe<2+> and removing the impurities from the solution at the same time; a step B of liquid and solid separation, which is to filter the solution obtained by the step A to obtain reduced and purified solution and reduced and purified slag; and a step C of replacing precipitated indium, which is to add zinc scum into the reduced and purified solution obtained by the step B to replace the precipitated indium, filtering to obtain filtrate and indium-enriched slag, recovering indium from the enriched slag and returning the filtrate to a zinc system to recovery zinc. The method is mainly used in wet-method zinc making plants for enriching and recovering indium from zinc oxide acid supernate.
Description
Technical field
The present invention relates to a kind of method of enriching and reclaiming indium, particularly a kind of from oxidation zincic acid supernatant the method for enriching and reclaiming indium.
Technical background
Indium belongs to eare scattered metals, because it has very unique and good physics and chemical property, be widely used in high-tech areas such as robot calculator, the energy, electronics, photoelectricity, national defense and military, space flight and aviation, nuclear industry, chemical industry and modern information industry, and make industry such as fusible alloy.Almost do not find both at home and abroad independent indium mineral deposit up to now and based on the mineral deposit of indium, most of indium is present in zink sulphide and the lead glance with rare diffusing state.Therefore, most of by product one indium enrichment slag that reclaims the raw material of indium from output in the lead-zinc smelting process.Be the leached mud that produces of zinc metallurgy process through Rotary Kiln volatilization output zinc oxide, zinc oxide obtains heavy indium slag through neutral, the acid leaching again through displacement or neutralization then, also is indium enrichment slag.
At present, the technology of enriching and reclaiming indium is directly to adopt in heavy indium of zinc dust precipitation or the zinc-oxide calcine and heavy indium from oxidation zincic acid supernatant (the ?leached mud is through Rotary Kiln volatilization output zinc oxide, and zinc oxide is through neutral, acid leaching, clear soln then).The heavy indium technology of zinc dust precipitation need expend a large amount of zinc powders, and enrichment per kilogram indium zinc powder unit consumption is 60～70kg, and cost is higher; And because zinc powder activity is big, speed of response is fast, easily produces the AsH of a large amount of severe toxicity
3Gas adds zinc powder simultaneously for preventing blast, must add zinc powder limit Jia Shui in the limit, has also reduced heavy indium efficient.Though in the zinc-oxide calcine and heavy indium technology cost low, because of Fe in the zinc-oxide calcine and other impurity component height, it is low to make the indium enrichment slag of output contain the In grade, indium enrichment slag contains Fe and other foreign matter content height, and is difficult to filter.Nowadays, because foreign matter contents such as indium grade reduction and Fe, Cu raise in the raw material, directly adopt the heavy indium of zinc dust precipitation and the heavy two kinds of technologies of indium of zinc-oxide calcine to be difficult to obtain the higher indium enrichment slag of grade, and that indium enrichment slag contain indium is low, the foreign matter content height increases the cost recovery of follow-up indium greatly.Therefore, in the prior art from oxidation zincic acid supernatant enriching and reclaiming indium technology be difficult to obtain the indium enrichment slag that the In grade is higher, foreign matter content is lower, how obtaining the indium enrichment slag that grade is higher, foreign matter content is lower and reduce production costs from above-mentioned raw materials is to remain the problem further explored.
Summary of the invention
The object of the present invention is to provide a kind of from oxidation zincic acid supernatant the method for enriching and reclaiming indium, it can improve indium enrichment slag indium grade effectively, reduces the content of impurity F e etc., and reduces the cost of enriching and reclaiming indium.Be particularly suitable for zinc hydrometallurgy producer enriching and reclaiming indium from the zinc metallurgy by product.
For achieving the above object, technical solution of the present invention is: a kind of from oxidation zincic acid supernatant the method for enriching and reclaiming indium, it is characterized in that following steps:
A, reduction purify, and iron powder is put in the oxidation zincic acid supernatant, with Fe
3+Be reduced into Fe
2+And remove impurity in the solution simultaneously;
B, liquid-solid separation, the solution that steps A is obtained filters, and the scavenging solution that obtains reducing purifies slag with reduction;
C, the heavy indium of displacement, the reduction scavenging solution that step B is obtained adds the heavy indium of zinc dross displacement, filters and obtains filtrate and indium enrichment slag, and this enrichment slag is sent to the recovery indium, and filtrate is returned the receipts ?that unite back of ?system.
The invention has the beneficial effects as follows:
The present invention adds iron powder with oxidation zincic acid supernatant earlier can be with Fe
3+Be reduced into Fe
2+With remove impurity such as Cu, Bi, and then, obtain indium enrichment slag with the heavy indium of zinc dross.Above-mentioned reductive mechanism is to utilize the stronger relatively reductibility of a certain element with the relative more weak element reduction of another reductibility, and its valency is reduced, and reaches the reductive purpose.The mechanism of above-mentioned purification is to utilize the lower material of the current potential metal ion that current potential is higher relatively to cement out from solution, makes the impurity that cements out form solid slag, thereby reaches the purpose of purification.
Oxidation zincic acid supernatant is after reduction and purifying, and when zinc dross sank indium, the chance that impurity such as Fe, Cu, Bi enter indium enrichment slag greatly reduced.The heavy indium of zinc dross is compared with the heavy indium of zinc powder has following advantage: the one, save a large amount of zinc powders, the production cost of promptly saving a large amount of zinc powder and being brought; The 2nd, zinc is smelted manufacturer, zinc dross is directly used in heavy indium, and just need not return boiling roaster can reclaim zinc in the same old way, saves the zinc dross roasting and reclaims the required energy consumption of zinc; The 3rd, add the zinc dross ratio and add zinc powder safety, add zinc powder for preventing blast, must add zinc powder limit Jia Shui in the limit.The heavy indium of zinc dross is compared with the heavy indium of zinc-oxide calcine has following advantage: the one, and it is higher that the indium enrichment slag that the heavy indium of zinc dross obtains contains In, and foreign matter content is lower; The 2nd, zinc-oxide calcine sinks indium, and the In of sour supernatant and impurity such as Fe, Cu all change in the heavy indium slag with the form of oxyhydroxide, and slag is difficult to filter etc.
The present invention has realized that oxidation zincic acid supernatant uses the novel process of zinc dross enriching and reclaiming indium again through the reduction of Fe powder, if oxidation zincic acid supernatant contains indium more than 450mg/L, then described indium enrichment slag contains In and can reach more than 2.0%, and heavy indium slag contains Fe＜2.0%, contain Cu＜0.15%, contain Bi＜0.20%, contain Zn25～30%, be higher-grade, low impurity indium enrichment slag.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention and embodiment thereof are described in further detail.
Referring to accompanying drawing, the invention is characterized in following steps:
A, reduction purify, and iron powder is put in the oxidation zincic acid supernatant, with Fe
3+Be reduced into Fe
2+And remove impurity in the solution simultaneously;
B, liquid-solid separation, the solution that steps A is obtained filters, and the scavenging solution that obtains reducing purifies slag with reduction;
C, the heavy indium of displacement, the reduction scavenging solution that step B is obtained adds the heavy indium of zinc dross displacement, filters and obtains filtrate and indium enrichment slag, and this enrichment slag is sent to the recovery indium, and filtrate is returned the receipts ?that unite back of ?system.
Technical scheme of the present invention is: adopt the Fe powder to the Fe in the oxidation zincic acid supernatant
3+Be reduced into Fe
2+, simultaneously impurity such as Cu, Bi are removed, filter and obtain reducing scavenging solution and reduction purification slag.Purify in the liquid of back toward reduction then and add zinc dross, the control endpoint pH, obtain the indium enrichment slag that indium grade is higher, foreign matter content is lower, the condition that adds the reduction of Fe powder and purify is: 50～70 ℃ of temperature, time 30～50min, add the Fe powder in continuous stirring condition, Fe powder add-on is Fe in the sour supernatant
3+Measure a false add Cu content summation 1.1～1.3 times, the granularity of zinc dross is at-120～-60 orders, contain zinc in the zinc dross greater than 80%, the condition that adds the heavy indium of zinc dross is: 65～75 ℃ of temperature, time 1.0～2.0h, add zinc dross in continuous stirring condition, the zinc dross add-on is controlled by endpoint pH, and the heavy indium endpoint pH of zinc dross is controlled at 4.6～5.0.If oxidation zincic acid supernatant contains indium more than 450mg/L, then described indium enrichment slag contains In and can reach more than 2.0%, and heavy indium slag contains Fe＜2.0%, contains Cu＜0.15%, contains Bi＜0.20%, contains Zn25～30%, is higher-grade, low impurity indium enrichment slag.
Principle of the present invention is:
Reduction is to utilize the stronger relatively reductibility of a certain element with the relative more weak element reduction of another reductibility, and its valency is reduced, and reaches the reductive purpose.Low sour supernatant reduction is exactly to utilize reductive agent will hang down Fe in the sour supernatant
3+Be reduced into Fe
2+
Displacement is to utilize the negative more material of current potential that the metal ion of the relative calibration of current potential is cemented out from solution, the metal that cements out is retained in the slag, thereby reaches the metathetical purpose.The heavy indium of zinc dross displacement is exactly that the In that utilizes the zinc in the zinc dross will hang down in the liquid of sour supernatant reduction back replaces to get off to change in the slag.The principal reaction formula is:
Fe+Cu
2+＝Fe
2++Cu
Fe+2Fe
3+＝3Fe
2+
3Fe+2Bi
3+＝2Bi+3Fe
2+
Fe+2H
+＝Fe
2++H
2↑
Zn+Cu
2+＝Zn
2++Cu
Zn+2Fe
3+＝2Fe
2++Zn
2+
3Zn+2Bi
3+＝2Bi+3Zn
2+
3Zn+2In
3+＝2In+3Zn
2+
Zn+2H
+＝Zn
2++H
2↑
ZnO+2H
+＝Zn
2++H
2O
Below provide embodiments of the invention:
Embodiment 1:
Adopt the present invention's enriching and reclaiming indium from oxidation zincic acid supernatant, 50 liters of oxidation zincic acid supernatants, its component and concentration: In0.55g/L, Fe
2+2.15g/L, Fe
3+17.92g/L, As1.67g/L, Cu1.36g/L, Bi0.048g/L, H
2SO
420.31g/L; Zinc dross main component and weight percent are: Zn87.88%, Fe0.062%; Add the Fe powder in oxidation zincic acid supernatant, reduction of Fe powder and the actual conditions that purifies are: 50 ℃ of temperature, and time 50min adds the Fe powder in continuous stirring condition, and Fe powder add-on is Fe in the sour supernatant
3+Measure a false add Cu content summation 1.1 times.Filtration obtains reduction purification back liquid and reduction purifies slag; Purify toward the reduction of filtering gained that to add granularity in the liquid of back be-60 purpose zinc dross, the actual conditions that adds the heavy indium of zinc dross is: 65 ℃ of temperature, and time 2.0h adds zinc dross in continuous stirring condition, the zinc dross add-on is controlled by endpoint pH, and endpoint pH is controlled at 4.6;
Oxidation zincic acid supernatant is handled through above-mentioned steps, and the indium enrichment slag that obtains contains In2.12%, contains Zn28.56%, and impurity F e, Cu, Bi content are respectively 1.98%, 0.14% and 0.13%.
Embodiment 2:
Adopt the present invention's enriching and reclaiming indium from oxidation zincic acid supernatant, 50 liters of oxidation zincic acid supernatants, its component and concentration: In0.55g/L, Fe
2+2.15g/L, Fe
3+17.92g/L, As1.67g/L, Cu1.36g/L, Bi0.048g/L, H
2SO
420.31g/L; Zinc dross main component and weight percent are: Zn87.88%, and Fe0.062% adds the Fe powder in oxidation zincic acid supernatant, reduction of Fe powder and the actual conditions that purifies are: 60 ℃ of temperature, time 40min adds the Fe powder in continuous stirring condition, and Fe powder add-on is Fe in the sour supernatant
3+Measure a false add Cu content summation 1.3 times.Liquid and reducing slag after filtration obtains reducing; Purify toward the reduction of filtering gained that to add granularity in the liquid of back be-80 purpose zinc dross, the actual conditions that adds the heavy indium of zinc dross is: 70 ℃ of temperature, time 2.0h, add zinc dross in continuous stirring condition, the zinc dross add-on is controlled by endpoint pH, and endpoint pH is controlled at 4.8, oxidation zincic acid supernatant is handled through above-mentioned steps, the indium enrichment slag that obtains contains In2.28%, contains Zn27.72%, and impurity F e, Cu, Bi content are respectively 1.85%, 0.12% and 0.14%.
Embodiment 3:
50 liters of oxidation zincic acid supernatants, its component and concentration: In0.55g/L, Fe
2+2.15g/L, Fe
3+17.92g/L, As1.67g/L, Cu1.36g/L, Bi0.048g/L, H
2SO
420.31g/L; Zinc dross main component and weight percent are: Zn87.88%, and Fe0.062% adds the Fe powder in oxidation zincic acid supernatant, reduction of Fe powder and the actual conditions that purifies are: 70 ℃ of temperature, time 30min adds the Fe powder in continuous stirring condition, and Fe powder add-on is Fe in the sour supernatant
3+Measure a false add Cu content summation 1.2 times.Liquid and reducing slag after filtration obtains reducing;
Purify toward the reduction of filtering gained that to add granularity in the liquid of back be-80 purpose zinc dross, the actual conditions that adds the heavy indium of zinc dross is: 75 ℃ of temperature, time 1.5h, constantly adding zinc dross under the stirring condition, the zinc dross add-on is controlled by endpoint pH, and endpoint pH is controlled at 4.8 oxidation zincic acid supernatants and handles through above-mentioned steps, and the indium enrichment slag that obtains contains In2.35%, contain Zn27.14%, impurity F e, Cu, Bi content are respectively 1.88%, 0.13% and 0.16%.
Embodiment 4:
50 liters of oxidation zincic acid supernatants, its component and concentration: In0.55g/L, Fe
2+2.15g/L, Fe
3+17.92g/L, As1.67g/L, Cu1.36g/L, Bi0.048g/L, H
2SO
420.31g/L; Zinc dross main component and weight percent are: Zn87.88%, and Fe0.062% adds the Fe powder in oxidation zincic acid supernatant, reduction of Fe powder and the actual conditions that purifies are: 70 ℃ of temperature, time 50min adds the Fe powder in continuous stirring condition, and Fe powder add-on is Fe in the sour supernatant
3+Measure a false add Cu content summation 1.1 times.Liquid and reducing slag after filtration obtains reducing; Purify toward the reduction of filtering gained that to add granularity in the liquid of back be-100 purpose zinc dross, the actual conditions that adds the heavy indium of zinc dross is: 75 ℃ of temperature, time 1.5h, add zinc dross in continuous stirring condition, the zinc dross add-on is controlled by endpoint pH, and endpoint pH is controlled at 5.0, oxidation zincic acid supernatant is handled through above-mentioned steps, the indium enrichment slag that obtains contains In2.48%, contains Zn26.75%, and impurity F e, Cu, Bi content are respectively 1.79%, 0.12% and 0.15%.
Embodiment 5:
50 liters of oxidation zincic acid supernatants, its component and concentration: In0.55g/L, Fe
2+2.15g/L, Fe
3+17.92g/L, As1.67g/L, Cu1.36g/L, Bi0.048g/L, H
2SO
420.31g/L; Zinc dross main component weight percent is: Zn87.88%, and Fe0.062% adds the Fe powder in oxidation zincic acid supernatant, reduction of Fe powder and the actual conditions that purifies are: 65 ℃ of temperature, time 50min adds the Fe powder in continuous stirring condition, and Fe powder add-on is Fe in the sour supernatant
3+Measure a false add Cu content summation 1.2 times.Liquid and reducing slag after filtration obtains reducing, purify toward the reduction of filtering gained that to add granularity in the liquid of back be-120 purpose zinc dross, the actual conditions that adds the heavy indium of zinc dross is: 75 ℃ of temperature, time 1h, add zinc dross in continuous stirring condition, the zinc dross add-on is controlled by endpoint pH, endpoint pH is controlled at 5.0, oxidation zincic acid supernatant is handled through above-mentioned steps, the indium enrichment slag that obtains contains In2.16%, contain Zn25.48%, impurity F e, Cu, Bi content are respectively 1.85%, 0.12% and 0.11%.
Claims (1)
1. the method for an enriching and reclaiming indium from oxidation zincic acid supernatant is characterized in that following steps:
A, reduction purify, and iron powder is put in the oxidation zincic acid supernatant, with Fe
3+Be reduced into Fe
2+And remove impurity in the solution simultaneously;
B, liquid-solid separation, the solution that steps A is obtained filters, and the scavenging solution that obtains reducing purifies slag with reduction;
C, the heavy indium of displacement, the reduction scavenging solution that step B is obtained adds the heavy indium of zinc dross displacement, filters and obtains filtrate and indium enrichment slag, and this enrichment slag is sent to the recovery indium, and filtrate is returned the receipts ?that unite back of ?system.
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|---|---|---|---|
| CN201010583278A CN101994009B (en) | 2010-12-10 | 2010-12-10 | Method for enriching and recovering indium from zinc oxide acid supernate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120287A (en) * | 2014-06-30 | 2014-10-29 | 蒙自矿冶有限责任公司 | Technique for enriching and recovering indium and associated copper from low-concentration indium-containing solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104884A (en) * | 2007-08-09 | 2008-01-16 | 株洲冶炼集团股份有限公司 | Method for leaching, enriching and reclaiming indium from lead-zinc smelting by-product zinc oxide |
| CN101289712A (en) * | 2008-05-27 | 2008-10-22 | 株洲冶炼集团股份有限公司 | Process for recovering indium from indium-containing material |
-
2010
- 2010-12-10 CN CN201010583278A patent/CN101994009B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104884A (en) * | 2007-08-09 | 2008-01-16 | 株洲冶炼集团股份有限公司 | Method for leaching, enriching and reclaiming indium from lead-zinc smelting by-product zinc oxide |
| CN101289712A (en) * | 2008-05-27 | 2008-10-22 | 株洲冶炼集团股份有限公司 | Process for recovering indium from indium-containing material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120287A (en) * | 2014-06-30 | 2014-10-29 | 蒙自矿冶有限责任公司 | Technique for enriching and recovering indium and associated copper from low-concentration indium-containing solution |
| CN104120287B (en) * | 2014-06-30 | 2015-06-24 | 蒙自矿冶有限责任公司 | Technique for enriching and recovering indium and associated copper from low-concentration indium-containing solution |
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|---|---|
| CN101994009B (en) | 2012-10-03 |
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