CN108130431B - A kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach - Google Patents
A kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach Download PDFInfo
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- CN108130431B CN108130431B CN201711256359.5A CN201711256359A CN108130431B CN 108130431 B CN108130431 B CN 108130431B CN 201711256359 A CN201711256359 A CN 201711256359A CN 108130431 B CN108130431 B CN 108130431B
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- germanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a kind of methods that rich germanium zinc concentrate oxygen leaching inhibits germanium to leach, belong to non-ferrous metal field of hydrometallurgy, processing step are as follows: 1) -320 mesh richness germanium zinc concentrates are subjected to one section of oxygen leaching, two sections of oxygen leaching liquids are added, fill into sulfuric acid, it is passed through industrial oxygen, stagnation pressure, reaction temperature, extraction time, filtering are controlled, one section of filter cake enters two sections of oxygen leachings, the neutralized further removing iron of one section of filtrate, germanium, electrowinning zinc after zincification powder purification and impurity removal；2) one section of oxygen filter-press residues carries out two sections of oxygen leachings, controls 20~30g/L of acid eventually, is passed through industrial oxygen, control 1.0~1.2MPa of stagnation pressure, 140~150 DEG C of reaction temperature, extraction time 1.0h, filtering, two sections of leached mud recycling sulphur, lead, silver and germanium, two sections of leachates return to one section of oxygen leaching.The method of the present invention inhibits germanium to leach in rich germanium zinc concentrate oxygen leaching, germanium is enriched with into leached mud, when solving rich germanium zinc concentrate oxygen leaching liquid subsequent processing the problems such as long flow path, complex process, high neutralizer consumption.
Description
Technical field
The invention belongs to non-ferrous metal field of hydrometallurgy, and in particular to a kind of richness germanium zinc concentrate oxygen leaching inhibition germanium leaching
Method out.
Background technique
When rich germanium zinc concentrate oxygen leaching, according to the technical parameter difference for leaching control, 70~90% germanium quilt in zinc concentrate
It is leached into leachate, leachate need to remove acid, iron, arsenic and germanium in solution using neutralization, oxidation before purification and impurity removal,
It when neutralizing, aoxidizing, if Ge content is high in solution, will lead to except germanium is not thorough, liquid requirement before purification, and germanium is not achieved in neutralizer
Neutralization iron dross removing is dispersed into be difficult to recycle.Therefore, numerous researchers and enterprise technology personnel think that oxygen pressure technology is uncomfortable
It closes and handles rich germanium zinc concentrate.
In Chinese patent " a kind of process of extracting germanium from germanium-containing material by pressure leaching " (publication number CN101205572A),
One section of pressure leaching of rich germanium zinc concentrate is obtained into germanium-containing solution, the heavy germanium of neutralizer is added in germanic liquid, obtains germanium enrichment slag, is enriched with slag
Germanium is leached again, passes through extraction, back extraction Ti recovery rich in germanium liquid.This method process is tediously long, germanium extractant source is narrow, it is difficult to industrialization
It promotes and applies.
(Hunan is coloured for document " technical studies of two sections of adverse current oxygen leaching principles of zinc sulfide concentrates and synthetical recovery gallium germanium "
Metal, the 1st phase of volume 25) in, using two sections of adverse current oxygen leachings, gallium, germanium are leached into one section of leaching of 10~15g/L containing acid
In liquid, using zinc dust precipitation, germanium enters replacement slag rate 79.27%, replacement slag is baked, chlorinated distillation Ti recovery, and germanium overall recovery is
65%.For this method in zinc dust precipitation, exist makes zinc powder consumption is big, generates a large amount of arsine gas to easily cause because solution contains sour height
The problems such as occupational health hazards, zinc dust precipitation germanium are not thorough.
Summary of the invention
In place of the present invention handles rich germanium zinc concentrate the deficiencies in the prior art for oxygen leaching, a kind of new processing is proposed
Method, in oxygen leaching, inhibit germanium leach, germanium is enriched in oxygen leaching slag, leached mud can after flotation sulphur, germanium into
Enter leaded, silver-colored etc. flotation tailing, when tailing recycles lead silver by pyrogenic process, germanium is enriched with to be recycled into flue dust.
The invention is realized by the following technical scheme, and specific implementation step is as follows:
1) one section of oxygen leaching precipitated iron, germanium
- 320 mesh richness germanium zinc concentrates are subjected to one section of oxygen leaching, two sections of oxygen leaching liquids are added, fills into sulfuric acid, is passed through work
Industry oxygen, control 0.6~0.8MPa of stagnation pressure, 130~150 DEG C of reaction temperature, 0.75~1.25h of extraction time, filter ore pulp, one
Section filter residue enters two sections of oxygen leachings, the neutralized further removing iron of one section of filtrate, germanium, electrowinning zinc after zincification powder purification and impurity removal；
2) two sections of oxygen leaching zinc
One section of oxygen filter-press residues carries out two sections of oxygen leachings, and sulfuric acid is added, and controls 20~30g/L of acid eventually, is passed through industrial oxygen,
1.0~1.2MPa of stagnation pressure is controlled, 140~150 DEG C of reaction temperature, extraction time 1.0h, filters ore pulp, can be returned from two sections of leached muds
Sulphur, lead, silver and germanium are received, two sections of leachates return to one section of oxygen leaching.
Preferably, controlling sulphuric acid by the consumption acid of zinc leaching rate 30~70% in step 1).
Preferably, terminal pH3.0~4.0 are leached in control in step 1).
One section of oxygen leaching process can precipitate the foreign metal in two sections of oxygen leaching liquids, and it is lower to obtain iron content, arsenic, germanium
Leachate mitigates the difficulty of one section of subsequent removal of impurities of oxygen leaching liquid and neutralizes the yield of slag, while germanium being made to enter oxygen pressure as far as possible
Leached mud, avoids being dispersed into and neutralizes slag and be difficult to recycle.
Because acid amount is insufficient, early period is reacted, the leaching of germanium is suppressed, and is reacted the middle and later periods, and the iron in ore pulp is with ferrovanadium (straw colour
Siderotil) Precipitation.
3Fe2(SO4)3+14H2O=(H3O)2Fe6(SO4)4(OH)12+5H2SO4
The germanium and arsenic brought into two sections of leachates are adsorbed with corresponding ion in isomorph substitution ferrovanadium or by ferrovanadium, with
Iron precipitates simultaneously；The sulfuric acid that ferrovanadium releases when being precipitated, continuation reacts with zinc excessive in zinc concentrate to be consumed, and is finally made
One section of oxygen leaching endpoint pH is controlled to 3.0~4.0.
Two sections of maximum Leaching Zincs of oxygen leaching process energy, while being controlled in zinc concentrate by controlling whole acid content
Germanium is not dissolved out largely, is not dissolved out with the germanium that siderotil precipitates again in one section of oxygen leaching, obtains higher zinc extracting rate
With lower germanium leaching rate, it is enriched with germanium in slag.
Beneficial effects of the present invention:
Germanium, by inhibiting germanium to leach, is enriched to oxygen leaching slag in rich germanium zinc concentrate oxygen leaching by the method for the present invention
In, when solving rich germanium zinc concentrate oxygen leaching liquid subsequent processing the problems such as long flow path, complex process, high neutralizer consumption.
Specific embodiment
Embodiment 1
(1) one section of oxygen leaching precipitated iron, germanium
- 320 mesh richness germanium zinc concentrates (Zn53.14%, Ge0.0082%) are put into autoclave, two sections of oxygen leaching liquids are added,
Sulfuric acid is filled by zinc concentrate zinc leaching rate 70%, is passed through oxygen, stagnation pressure 0.6MPa is controlled, 130 DEG C of reaction temperature, is stirred to react
0.75h filters ore pulp, obtains one section of filtrate and one section of filter cake, one section of filtrate component: Zn152.6g/L, Fe0.08g/L,
Ge2.19mg/L, pH3.0；
(2) two sections of oxygen leaching zinc
One section of filter cake is put into autoclave, by acid 30g/L is incorporated sulfuric acid eventually after reaction, oxygen is passed through, controls stagnation pressure
1.0MPa 140 DEG C of reaction temperature, is stirred to react 1.0h, filters ore pulp, obtain two sections of filtrates and two sections of filter cakes, two sections of filtrates
(Fe4.58g/L, Ge11.6mg/L, H2SO429.87g/L) return to one section of leaching, two sections of filter cake recycling sulphur, lead, silver and germanium.
After two sections are leached, final zinc leaching rate is 98.27%, and germanium leaching rate is 9.82%.
Embodiment 2
(1) one section of oxygen leaching precipitated iron, germanium
- 320 mesh richness germanium zinc concentrates (Zn45.66%, Ge0.0169%) are put into autoclave, two sections of oxygen leaching liquids are added,
Sulfuric acid is filled by zinc concentrate zinc leaching rate 50%, is passed through oxygen, stagnation pressure 0.7MPa is controlled, 140 DEG C of reaction temperature, is stirred to react
1.0h filters ore pulp, obtains one section of filtrate and one section of filter cake, one section of filtrate component: Zn147.3g/L, Fe0.05g/L,
Ge2.47mg/L, pH3.5；
(2) two sections of oxygen leaching zinc
One section of filter cake is put into autoclave, by acid 25g/L is incorporated sulfuric acid eventually after reaction, oxygen is passed through, controls stagnation pressure
1.1MPa 145 DEG C of reaction temperature, is stirred to react 1.0h, filters ore pulp, obtain two sections of filtrates and two sections of filter cakes, two sections of filtrates
(Fe3.34g/L, Ge9.88mg/L, H2SO426.47g/L) return to one section of leaching, two sections of filter cake recycling sulphur, lead, silver and germanium.
After two sections are leached, final zinc leaching rate is 97.34%, and germanium leaching rate is 7.65%.
Embodiment 3
(1) one section of oxygen leaching precipitated iron, germanium
- 320 mesh richness germanium zinc concentrates (Zn49.02%, Ge0.0253%) are put into autoclave, two sections of oxygen leaching liquids are added,
Sulfuric acid is filled by zinc concentrate zinc leaching rate 30%, is passed through oxygen, stagnation pressure 0.8MPa is controlled, 150 DEG C of reaction temperature, is stirred to react
1.25h filters ore pulp, obtains one section of filtrate and one section of filter cake, one section of filtrate component: Zn149.4g/L, Fe0.04g/L,
Ge2.35mg/L, pH4.0；
(2) two sections of oxygen leaching zinc
One section of filter cake is put into autoclave, by acid 20g/L is incorporated sulfuric acid eventually after reaction, oxygen is passed through, controls stagnation pressure
1.2MPa 150 DEG C of reaction temperature, is stirred to react 1.0h, filters ore pulp, obtain two sections of filtrates and two sections of filter cakes, two sections of filtrates
(Fe4.33g/L, Ge12.27mg/L, H2SO419.52g/L) return to one section of leaching, two sections of filter cake recycling sulphur, lead, silver and germanium.
After two sections are leached, final zinc leaching rate is 97.92%, and germanium leaching rate is 5.65%.
Germanium, by inhibiting germanium to leach, is enriched to oxygen leaching slag in rich germanium zinc concentrate oxygen leaching by the method for the present invention
In, when solving rich germanium zinc concentrate oxygen leaching liquid subsequent processing the problems such as long flow path, complex process, high neutralizer consumption.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (2)
1. a kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach, is implemented by following steps:
1) -320 mesh richness germanium zinc concentrates are carried out one section of oxygen leaching, two sections of oxygen pressures are added by one section of oxygen leaching precipitated iron, germanium
Leachate fills into sulfuric acid, is passed through industrial oxygen, controls stagnation pressure 0 .6~0 .8MPa, and 130~150 DEG C of reaction temperature, when leaching
Between the .25h of 0 .75~1, leach terminal pH3 .0~4 .0, filter ore pulp, one section of filter residue enters two sections of oxygen leachings, one section of filtrate
Neutralized further removing iron, germanium, electrowinning zinc after zincification powder purification and impurity removal；
2) two sections of oxygen leaching zinc, one section of oxygen filter-press residues carry out two sections of oxygen leachings, sulfuric acid are added, and control 20~30g/ of acid eventually
L is passed through industrial oxygen, controls stagnation pressure 1 .0~1 .2MPa, 140~150 DEG C of reaction temperature, 1 .0h of extraction time, filters mine
Slurry, two sections of leached muds recycling sulphur, lead,
Silver and germanium, two sections of leachates return to one section of oxygen leaching.
2. the method that a kind of rich germanium zinc concentrate oxygen leaching according to claim 1 inhibits germanium to leach, it is characterized in that: step
1) in, sulphuric acid is controlled by the consumption acid of zinc leaching rate 30~70%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711256359.5A CN108130431B (en) | 2017-12-04 | 2017-12-04 | A kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach |
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| CN201711256359.5A CN108130431B (en) | 2017-12-04 | 2017-12-04 | A kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach |
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| CN108130431A CN108130431A (en) | 2018-06-08 |
| CN108130431B true CN108130431B (en) | 2019-09-20 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795795B (en) * | 2020-12-15 | 2023-10-03 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation |
| CN113088710A (en) * | 2021-03-29 | 2021-07-09 | 云南驰宏资源综合利用有限公司 | Method for separating copper and germanium from copper and germanium replacement slag |
| CN113832346B (en) * | 2021-09-16 | 2023-07-21 | 云南驰宏资源综合利用有限公司 | Method for efficiently and simply treating germanium-containing zinc leaching residues |
| CN114959260B (en) * | 2022-06-13 | 2024-03-15 | 昆明理工大学 | Oxygen pressure leaching method for low-iron zinc concentrate |
| CN115386732A (en) * | 2022-09-06 | 2022-11-25 | 昆明冶金研究院有限公司 | Method for efficiently recycling zinc, germanium and indium in zinc oxide smoke dust |
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