CN110117723A - A kind of richness germanium zinc oxide fumes leaching method - Google Patents
A kind of richness germanium zinc oxide fumes leaching method Download PDFInfo
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- CN110117723A CN110117723A CN201910387083.7A CN201910387083A CN110117723A CN 110117723 A CN110117723 A CN 110117723A CN 201910387083 A CN201910387083 A CN 201910387083A CN 110117723 A CN110117723 A CN 110117723A
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- leaching
- zinc
- germanium
- zinc oxide
- underflow
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- 238000002386 leaching Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000003517 fume Substances 0.000 title claims abstract description 47
- GIEKGJMFQVAGJK-UHFFFAOYSA-N [O-2].[Zn+2].[Ge+2].[O-2] Chemical compound [O-2].[Zn+2].[Ge+2].[O-2] GIEKGJMFQVAGJK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011701 zinc Substances 0.000 claims abstract description 97
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 91
- 239000002253 acid Substances 0.000 claims abstract description 47
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 46
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 24
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- MRZMQYCKIIJOSW-UHFFFAOYSA-N germanium zinc Chemical compound [Zn].[Ge] MRZMQYCKIIJOSW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 62
- 238000009854 hydrometallurgy Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000005868 electrolysis reaction Methods 0.000 claims description 30
- 239000002699 waste material Substances 0.000 claims description 29
- 238000000227 grinding Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 2
- 235000019504 cigarettes Nutrition 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 32
- 230000008569 process Effects 0.000 abstract description 26
- 229910052742 iron Inorganic materials 0.000 abstract description 21
- 239000011787 zinc oxide Substances 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 8
- -1 iron ion Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 3
- 235000021110 pickles Nutrition 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 15
- 238000011084 recovery Methods 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000009858 zinc metallurgy Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of rich germanium zinc oxide fumes leaching methods, belong to technical field of wet metallurgy.The method that the present invention is leached by two sections, three steps control, zinc oxide fumes are divided into when one section of leaching and leaches raw material, neutralize two class of raw material, the two class slags (underflow) that one section is leached are subjected to collaboration leaching when two sections of leachings, the acidity (20 ~ 40g/L of terminal acidity) that first section first carries out zinc oxide fumes leaches (i.e. low acid control oxygen leaches), then again respectively to the Process configuration that pickle liquor and acidleach underflow carry out neutralization reduction, collaboration is leached, and substep realizes efficient leaching, the reduction of iron ion, the control of leachate pH of zinc germanium.On the basis of first section first carries out weak acid (terminal pH1.5 ~ 3.5) leaching, the process flow of high acidic oils again, optimize the extract technology of zinc oxide fumes, leach Leaching Systems acid concentration between peracid (80 ~ 120g/L of terminal acidity) leaching between traditional weak acid (terminal pH1.5 ~ 3.5), oxidation to make reaction condition be conducive to oxygen to sulfide, to improve zinc, germanium leaching rate.
Description
Technical field
The present invention relates to a kind of rich germanium zinc oxide fumes leaching methods, belong to technical field of wet metallurgy.
Background technique
Germanium is widely used in high-tech area because of its unique physical and chemical properties as dissipated metal.In nature
The germanium deposit that rarely can independently exploit, currently, the recycling of germanium is industrial mainly from zinc abstraction, in the hydrometallurgy stream of zincblende
Cheng Zhong, germanium can be enriched in zinc leaching residue, and zinc leaching residue has become the valuable source of recycling gallium germanium.The method of germanic zinc leaching residue Ti recovery
In addition to this predominantly fire reduction volatility process and wet process high temperature high acidic oils further include the direct oxygen pressure leaching of germanic zinc concentrate
Out.For example, Yunnan Chihong Zinc & Germanium Co., Ltd. is using conventional zinc abstraction technique and the germanic oxidation zinc technology of fuming furnace volatilization；
Japanese Iijima smeltery leaches the gallium germanium in the slag using the liquid sulfur dioxide reduction acid-hatching of young eggs, Beijing Mine and Metallurgy General Inst (from
Zinc leaching residue mesohigh leaches the research of gallium germanium, non-ferrous metal (Smelting Part), 8 phases in 2012) carry out sulfur dioxide high pressure also
The research work that original leaches, Yunnan Hua Lian Xin Yin limited liability company are effectively to recycle valuable metal in zinc leaching residue, construction
The smelting process of sulfur dioxide high pressure reducing leaching zinc leaching residue；Guangdong Shaoguan smeltery Dan Xia uses zinc sulfide concentrates direct two
It holds high temperature acid leaching process (synthetical recovery gallium and germanium, non-ferrous metal, the 4th phase in 2009 in the smeltery Cong Danxia zinc leaching residue).
However, since the zinc abstraction technique in current China is based on traditional common process, the extraction raw material master of germanium
If from germanic zinc oxide fumes.Germanic zinc oxide fumes are to handle zinc hydrometallurgy, pyrometallurgical smelting of lead using pyrogenic process fuming volatility process
A kind of intermediate raw material for mainly containing the valuable metals such as zinc, lead, germanium, silver of output, the processing method generallyd use at present after slag
It is first to carry out sulphuric leaching, leaches finishing slag (lead smelting gas) and send pyrogenic process recycling lead and silver, leachate carries out tannin sinking germanium, output germanium slag
Germanium concentrate is obtained by calcination, liquid neutralize except iron send purification and electroextraction zinc later after heavy germanium.But long-term production is real
It tramples and shows in conventional zinc metallurgical process, the long flow path of germanium recycling, and germanic zinc in zinc oxide, the rate of recovery of germanium are lower, zinc is only
85% or so；Germanium is less than 60%.Zinc is primarily present form in the mainly germanic zinc oxide fumes for causing the zinc germanium rate of recovery low
For variforms such as zinc oxide, zinc sulfate and zinc sulphide, and insoluble P is more, and zinc oxide fumes particle is larger, and granularity is not
Uniformly, lower using conventional treatment process zinc, germanium leaching rate.Therefore, the leaching rate of zinc, germanium how is improved, reduces and leaches finishing slag
The content of zinc, germanium in (lead smelting gas) is the key link for restricting zinc, the germanium rate of recovery.
In the prior art, the method for Ti recovery provides I section of atmospheric low-temperature Weak-acid leaching, II section of height from zinc oxide fumes
Two sections of counterflow leaching techniques of warm oxygen leaching, while leachate is restored using sodium sulfite；Zinc oxide fumes are efficient
The method for extracting zinc germanium provides I section of atmospheric low-temperature Weak-acid leaching, II section of oxygen forces down two sections of counterflow leaching works of warm high acidic oils
In comparison skill reduces the temperature of II section of oxygen leaching.Oxygen leaching can greatly improve zinc, germanium leaching rate, but compare normal pressure
Extract technology, required equipment requirement is high, and ferric iron concentration is not easy to control in leachate, and high concentration ferric iron is to postorder from leaching
Liquid Ti recovery is affected, and need to increase special reducing process to ensure the iron in leachate as ferrous iron.
Therefore, how to be realized under normal pressure system in the efficient Leaching Zinc of germanic zinc oxide fumes, germanium and synchronously control solution
Iron valence state simplifies production technology, does not have been reported that.
Summary of the invention
In view of the problems of the existing technology the present invention, provides a kind of rich germanium zinc oxide fumes leaching method, side of the present invention
Method is directed to the low problem of traditional two sections of counterflow leaching process flow leaching rates, is configured by optimization and adjusting process process, substep is real
Efficient leachings, the reduction of iron ion, the control of leachate pH of existing zinc germanium, zinc in solution smelting process, germanium it is efficient leach and
In leachate the problems such as ferric control, process flow is simple, low energy consumption, clean and environmental protection, is conducive to resource comprehensive utilization benefit
With.
A kind of richness germanium zinc oxide fumes leaching method, the specific steps are as follows:
(1) rich germanium zinc oxide fumes are uniformly mixed to obtain mixture A with sulphur content powder, water is added and sizes mixing, then carries out wet
Mill activation obtains the fine grinding ore pulp that smoke granularity is not more than 0.074mm；
(2) zinc hydrometallurgy electrolysis waste solution is added in the fine grinding ore pulp of step (1) and is uniformly mixed, be passed through oxygen, be in temperature
80 ~ 90 DEG C, low acid control 1.5 ~ 2.5h of oxygen Leach reaction obtains Weak-acid leaching liquid A and low sour underflow under stirring condition；
(3) the fine grinding ore pulp of step (1) is added in the Weak-acid leaching liquid A of step (2), is 70 ~ 80 DEG C, stirring condition in temperature
1.0 ~ 2.0h of lower neutralization reduction reaction obtains leachate B and neutralizes underflow；Leachate B carries out heavy germanium processing；
(4) the neutralization underflow of step (3), the low sour underflow of step (2) and zinc hydrometallurgy electrolysis waste solution are uniformly mixed, in temperature
2 ~ 3h of Leach reaction is cooperateed with to obtain high acidic oils liquid C and peracid underflow for peracid under 80 ~ 90 DEG C, stirring condition；High acidic oils liquid C
Substitution zinc hydrometallurgy electrolysis waste solution carries out low acid control oxygen Leach reaction in return step (2)；Peracid underflow carries out filters pressing and is pressed
Filter residue, filter-press residues mix with water and carry out low temperature pulp washing, centrifugal filtration obtains the wash water of germanium containing zinc and leach finishing slag, and zinc germanium is washed
Substitution water is sized mixing in water return step (1), and leaching finishing slag is zinc hydrometallurgy lead smelting gas.
The mass ratio of the rich germanium zinc oxide fumes of the step (1) and sulphur content powder is 1:(0.001 ~ 0.003).
The solid-to-liquid ratio kg:L of the rich germanium zinc oxide fumes of the step (1) and water is 1:(1 ~ 2).
The butt of step (2) the fine grinding ore pulp and the solid-to-liquid ratio kg:L of zinc hydrometallurgy electrolysis waste solution are 1:(5.5 ~ 7.5).
The butt of step (3) the fine grinding ore pulp and the solid-to-liquid ratio kg:L of Weak-acid leaching liquid A are (0.40 ~ 0.50): (5.5 ~
7.5)。
The step (4) neutralizes the butt, the butt of low sour underflow and the solid-to-liquid ratio kg of zinc hydrometallurgy electrolysis waste solution of underflow:
Kg:L is (0.20 ~ 0.30): (0.35 ~ 0.45): (5.5 ~ 7.5).
The solid-to-liquid ratio kg:L of the butt of filter-press residues and water is (0.55 ~ 0.65): (1.5 ~ 2.5) in the step (4).
When the richness germanium zinc oxide fumes are conventional wet lay zinc metallurgy slag, pyrometallurgical smelting of lead slag is handled using pyrogenic process fuming volatility process
Gained zinc smoke, wherein in addition to containing zinc and iron, germanic 0.05 ~ 0.20 wt.%, 2 ~ 8wt.% of sulfur-bearing；The zinc hydrometallurgy
Electrolysis waste solution is the zinc sulfate solution of 155 ~ 185g/L of sulfur acid of well known conventional wet lay zinc metallurgy electrolysis process output.
Contain 0.3 ~ 1g/L of ferric iron, 20 ~ 40g/L of sulfuric acid in the Weak-acid leaching liquid A；The low sour underflow containing zinc 10 ~
20wt.%；
The leachate B is less than 30mg/L containing ferric iron, and pH value is 2.5 ~ 3.5；It neutralizes underflow and contains 15 ~ 25 wt.% of zinc, iron content
5~10 wt.%；
The high acidic oils liquid C contains 0.5 ~ 1.5g/L of ferric iron, 80 ~ 120g/L of sulfuric acid, and peracid underflow is containing 5 ~ 10wt.% of zinc, germanic
0.02 ~ 0.03wt.%, 0.5 ~ 1.5wt.% of iron content；
The present invention leached by two sections, the method for three steps control, is divided into zinc oxide fumes when one section of leachings and is leached raw material, neutralization
Two class of raw material, two sections leach when by one section leach two class slags (underflow) carry out association's leaching, first section first carries out zinc oxide fumes
During acid (20 ~ 40g/L of terminal acidity) leaches (i.e. low acid control oxygen leaches), then carries out respectively to pickle liquor and acidleach underflow again
The Process configuration leached with reduction, collaboration, substep realize efficient leaching, the reduction of iron ion, the control of leachate pH of zinc germanium.
On the basis of traditional first section first carries out weak acid (terminal pH1.5 ~ 3.5) leaching, the then process flow of high acidic oils again, optimization
The first section leaching condition of zinc oxide fumes leaches Leaching Systems acid concentration between traditional weak acid (terminal pH1.5 ~ 3.5)
Between peracid (80 ~ 120g/L of terminal acidity) leaching, thus the oxidation for making reaction condition be conducive to oxygen to sulfide, to mention
Gao Xin, germanium leaching rate.
The beneficial effects of the present invention are:
(1) zinc of the present invention, germanium leaching rate are high, leaching are cooperateed with neutralize underflow by acidleach underflow, using in neutralization underflow
Sulfide oxidation in acidleach underflow is converted and is leached by ferric iron, is leached zinc, Ge content in finishing slag to reduce, is realized zinc, germanium
It efficiently leaches, more traditional first section first carries out weak acid (terminal pH1.5 ~ 3.5) leaching and then the again technique of high acidic oils, leaches
Rate can be improved 10% or so；
(2) present invention is easy to the separation of postorder zinc, germanium, iron: zinc oxide fumes is had by oneself by technique, to the acid of acidic leaching output
Immersion liquid carries out neutralization reduction, realizes the control of iron ion valence state, pH in leachate, ferric iron is less than 30mg/ in gained leachate
L, pH2.5 ~ 3.5 are easy to postorder and precipitate Ti recovery from leachate；
(3) present invention process and equipment are simple: the present invention uses normal pressure leaching technique, is not necessarily to compressive reaction kettle, adds compared to normal pressure-
Pressure process integration simplifies technical process, easy to operate, is easy to process control.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1: as follows with the rich germanium zinc oxide fumes main component that certain factory provides: Zn:47.26wt.%, Fe:5.03
Wt.%, S:7.98wt.%, Pb12.57 wt.%, Ge:506g/t, zinc hydrometallurgy electrolysis waste solution main component are as follows: H2SO4:
185g/L,Zn: 53g/L；
A kind of richness germanium zinc oxide fumes leaching method, the specific steps are as follows:
(1) 1.4kg richness germanium zinc oxide fumes are uniformly mixed to obtain mixture A with sulphur content powder, water is added to size mixing, then carried out
Wet-milling activates to obtain the fine grinding ore pulp that smoke granularity is not more than 0.074mm；The wherein matter of rich germanium zinc oxide fumes and sulphur content powder
Ratio is measured as 1:0.001, the solid-to-liquid ratio kg:L of rich germanium zinc oxide fumes and water is 1:2；
(2) 5.5L zinc hydrometallurgy electrolysis waste solution is added in the fine grinding ore pulp of step (1) and is uniformly mixed, be passed through oxygen (oxygen
Volumetric concentration is 99.9%), temperature is 85 DEG C, low acid control oxygen Leach reaction 2h obtains Weak-acid leaching liquid A and low under stirring condition
Sour underflow；Wherein the solid-to-liquid ratio kg:L of the butt of fine grinding ore pulp and zinc hydrometallurgy electrolysis waste solution is 1:5.5；In Weak-acid leaching liquid A
1g/L containing ferric iron, sulfuric acid 20g/L；The low sour underflow 20wt.% containing zinc；
(3) the fine grinding ore pulp of step (1) is added in the Weak-acid leaching liquid A of step (2), is 75 DEG C, under stirring condition in temperature
Reduction reaction 1.5h is neutralized to obtain leachate B and neutralize underflow；Leachate B carries out heavy germanium processing；The wherein butt of fine grinding ore pulp
Solid-to-liquid ratio kg:L with Weak-acid leaching liquid A is 0.40:5.5；Leachate B is less than 30mg/L, pH value 3.5 containing ferric iron；In
Contain 25 wt.% of zinc, 10 wt.% of iron content with underflow；
(4) the neutralization underflow of step (3), the low sour underflow of step (2) and zinc hydrometallurgy electrolysis waste solution are uniformly mixed, in temperature
Leach reaction 3h is cooperateed with to obtain high acidic oils liquid C and peracid underflow for peracid under 80 DEG C, stirring condition；High acidic oils liquid C is returned
Substitution zinc hydrometallurgy electrolysis waste solution carries out low acid control oxygen Leach reaction in step (2)；Peracid underflow carries out filters pressing and obtains filter-press residues,
Filter-press residues mix with water and carry out low temperature pulp washing, centrifugal filtration obtains the wash water of germanium containing zinc and leach finishing slag, and zinc germanium wash water returns
It returns substitution water in step (1) to size mixing, leaching finishing slag is zinc hydrometallurgy lead smelting gas；Wherein neutralize butt, the low acid of underflow
The solid-to-liquid ratio kg:kg:L of the butt of underflow and zinc hydrometallurgy electrolysis waste solution is 0.30:0.45:5.5, the butts of filter-press residues and water
Solid-to-liquid ratio kg:L is 0.55:2.5；High acidic oils liquid C 1.5g/L containing ferric iron, sulfuric acid 80g/L, peracid underflow 10wt.% containing zinc,
Germanic 0.02wt.%, iron content 1.5wt.%；
The present embodiment zinc leaching rate is 90.6%, and germanium leaching rate is 82.7%；It leaches finishing slag and contains zinc 9.87%, germanic 211g/t.
Embodiment 2: as follows with the rich germanium zinc oxide fumes main component that certain factory provides: Zn:47.17wt.%, Fe:4.03
Wt.%, S:6.45 wt.%, Pb11.96 wt.%, Ge:721g/t, zinc hydrometallurgy electrolysis waste solution main component are as follows: H2SO4:
165g/L,Zn: 49g/L；
A kind of richness germanium zinc oxide fumes leaching method, the specific steps are as follows:
(1) 1.45kg richness germanium zinc oxide fumes are uniformly mixed to obtain mixture A with sulphur content powder, water is added and sizes mixing, then
Wet-milling is carried out to activate to obtain the fine grinding ore pulp that smoke granularity is not more than 0.074mm；Wherein rich germanium zinc oxide fumes and sulphur content powder
Mass ratio be 1:0.002, the solid-to-liquid ratio kg:L of rich germanium zinc oxide fumes and water is 1:1.52；
(2) 6L zinc hydrometallurgy electrolysis waste solution is added in the fine grinding ore pulp of step (1) and is uniformly mixed, be passed through oxygen (carrier of oxygen
Product concentration is 80%), temperature is 90 DEG C, low acid control oxygen Leach reaction 1.5h obtains Weak-acid leaching liquid A and low acid under stirring condition
Underflow；Wherein the solid-to-liquid ratio kg:L of the butt of fine grinding ore pulp and zinc hydrometallurgy electrolysis waste solution is 1:6；Contain three in Weak-acid leaching liquid A
Valence iron 0.6g/L, sulfuric acid 30g/L；The low sour underflow 16wt.% containing zinc；
(3) the fine grinding ore pulp of step (1) is added in the Weak-acid leaching liquid A of step (2), is 80 DEG C, under stirring condition in temperature
Reduction reaction 1.0h is neutralized to obtain leachate B and neutralize underflow；Leachate B carries out heavy germanium processing；The wherein butt of fine grinding ore pulp
Solid-to-liquid ratio kg:L with Weak-acid leaching liquid A is 0.45:6；Leachate B is less than 30mg/L, pH value 3.0 containing ferric iron；It neutralizes
Underflow contains 21 wt.% of zinc, 7 wt.% of iron content；
(4) the neutralization underflow of step (3), the low sour underflow of step (2) and zinc hydrometallurgy electrolysis waste solution are uniformly mixed, in temperature
Leach reaction 2.5h is cooperateed with to obtain high acidic oils liquid C and peracid underflow for peracid under 90 DEG C, stirring condition；High acidic oils liquid C is returned
It returns substitution zinc hydrometallurgy electrolysis waste solution in step (2) and carries out low acid control oxygen Leach reaction；Peracid underflow carries out filters pressing and obtains filters pressing
Slag, filter-press residues mix with water and carry out low temperature pulp washing, centrifugal filtration obtains the wash water of germanium containing zinc and leach finishing slag, zinc germanium wash water
Substitution water is sized mixing in return step (1), and leaching finishing slag is zinc hydrometallurgy lead smelting gas；Wherein neutralize the butt, low of underflow
The solid-to-liquid ratio kg:kg:L of the butt of sour underflow and zinc hydrometallurgy electrolysis waste solution is 0.25:0.40:6, the butts of filter-press residues and water
Solid-to-liquid ratio kg:L is 0.61:2.2；High acidic oils liquid C 1.1g/L containing ferric iron, sulfuric acid 105g/L, peracid underflow contain zinc
8.6wt.%, germanic 0.028wt.%, iron content 1.2wt.%；
The present embodiment zinc leaching rate is 91.6%, and germanium leaching rate is 84.2%；It leaches finishing slag and contains zinc 8.57%, germanic 281g/t.
Embodiment 3: as follows with the rich germanium zinc oxide fumes main component that certain factory provides: Zn:45.33wt.%, Fe:3.22
Wt.%, S:2.05 wt.%, Pb13.89 wt.%, Ge:1972g/t, zinc hydrometallurgy electrolysis waste solution main component are as follows: H2SO4:
155g/L,Zn: 46g/L；
A kind of richness germanium zinc oxide fumes leaching method, the specific steps are as follows:
(1) 1.5kg richness germanium zinc oxide fumes are uniformly mixed to obtain mixture A with sulphur content powder, water is added and sizes mixing, then into
Row wet-milling activates to obtain the fine grinding ore pulp that smoke granularity is not more than 0.074mm；Wherein rich germanium zinc oxide fumes and sulphur content powder
Mass ratio is 1:0.003, and the solid-to-liquid ratio kg:L of rich germanium zinc oxide fumes and water is 1:1；
(2) 7.5L zinc hydrometallurgy electrolysis waste solution is added in the fine grinding ore pulp of step (1) and is uniformly mixed, be passed through oxygen (oxygen
Volumetric concentration is 92%), temperature is 80 DEG C, low acid control oxygen Leach reaction 2.5h obtains Weak-acid leaching liquid A and low under stirring condition
Sour underflow；Wherein the solid-to-liquid ratio kg:L of the butt of fine grinding ore pulp and zinc hydrometallurgy electrolysis waste solution is 1:7.5；In Weak-acid leaching liquid A
0.3g/L containing ferric iron, sulfuric acid 40g/L；The low sour underflow 10wt.% containing zinc；
(3) the fine grinding ore pulp of step (1) is added in the Weak-acid leaching liquid A of step (2), is 70 DEG C, under stirring condition in temperature
Reduction reaction 2.0h is neutralized to obtain leachate B and neutralize underflow；Leachate B carries out heavy germanium processing；The wherein butt of fine grinding ore pulp
Solid-to-liquid ratio kg:L with Weak-acid leaching liquid A is 0.50:7.5；Leachate B is less than 30mg/L, pH value 2.5 containing ferric iron；In
Contain 15 wt.% of zinc, iron content 5wt.% with underflow；
(4) the neutralization underflow of step (3), the low sour underflow of step (2) and zinc hydrometallurgy electrolysis waste solution are uniformly mixed, in temperature
Leach reaction 2h is cooperateed with to obtain high acidic oils liquid C and peracid underflow for peracid under 85 DEG C, stirring condition；High acidic oils liquid C is returned
Substitution zinc hydrometallurgy electrolysis waste solution carries out low acid control oxygen Leach reaction in step (2)；Peracid underflow carries out filters pressing and obtains filter-press residues,
Filter-press residues mix with water and carry out low temperature pulp washing, centrifugal filtration obtains the wash water of germanium containing zinc and leach finishing slag, and zinc germanium wash water returns
It returns substitution water in step (1) to size mixing, leaching finishing slag is zinc hydrometallurgy lead smelting gas；Wherein neutralize butt, the low acid of underflow
The solid-to-liquid ratio kg:kg:L of the butt of underflow and zinc hydrometallurgy electrolysis waste solution is 0.20:0.35:7.5, the butts of filter-press residues and water
Solid-to-liquid ratio kg:L is 0.65:1.5；High acidic oils liquid C 0.5g/L containing ferric iron, sulfuric acid 120g/L, peracid underflow 5wt.% containing zinc,
Germanic 0.03wt.%, iron content 0.5wt.%；
The present embodiment zinc leaching rate is 95.1%, and germanium leaching rate is 93.4%；It leaches finishing slag and contains zinc 5.17%, germanic 298g/t.
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Various change out.
Claims (7)
1. a kind of richness germanium zinc oxide fumes leaching method, which is characterized in that specific step is as follows:
(1) rich germanium zinc oxide fumes are uniformly mixed to obtain mixture A with sulphur content powder, water is added and sizes mixing, then carries out wet
Mill activation obtains the fine grinding ore pulp that smoke granularity is not more than 0.074mm；
(2) zinc hydrometallurgy electrolysis waste solution is added in the fine grinding ore pulp of step (1) and is uniformly mixed, be passed through oxygen, be in temperature
80 ~ 90 DEG C, low acid control 1.5 ~ 2.5h of oxygen Leach reaction obtains Weak-acid leaching liquid A and low sour underflow under stirring condition；
(3) the fine grinding ore pulp of step (1) is added in the Weak-acid leaching liquid A of step (2), is 70 ~ 80 DEG C, stirring condition in temperature
1.0 ~ 2.0h of lower neutralization reduction reaction obtains leachate B and neutralizes underflow；Leachate B carries out heavy germanium processing；
(4) the neutralization underflow of step (3), the low sour underflow of step (2) and zinc hydrometallurgy electrolysis waste solution are uniformly mixed, in temperature
2 ~ 3h of Leach reaction is cooperateed with to obtain high acidic oils liquid C and peracid underflow for peracid under 80 ~ 90 DEG C, stirring condition；High acidic oils liquid C
Substitution zinc hydrometallurgy electrolysis waste solution carries out low acid control oxygen Leach reaction in return step (2)；Peracid underflow carries out filters pressing and is pressed
Filter residue, filter-press residues mix with water and carry out low temperature pulp washing, centrifugal filtration obtains the wash water of germanium containing zinc and leach finishing slag, and zinc germanium is washed
Substitution water is sized mixing in water return step (1), and leaching finishing slag is zinc hydrometallurgy lead smelting gas.
2. rich germanium zinc oxide fumes leaching method according to claim 1, it is characterised in that: step (1) richness germanium zinc oxide cigarette
The mass ratio of dirt and sulphur content powder is 1:(0.001 ~ 0.003).
3. rich germanium zinc oxide fumes leaching method according to claim 1, it is characterised in that: step (1) richness germanium zinc oxide cigarette
The solid-to-liquid ratio kg:L of dirt and water is 1:(1 ~ 2).
4. rich germanium zinc oxide fumes leaching method according to claim 1, it is characterised in that: step (2) fine grinding ore pulp is done
The solid-to-liquid ratio kg:L of base and zinc hydrometallurgy electrolysis waste solution is 1:(5.5 ~ 7.5).
5. rich germanium zinc oxide fumes leaching method according to claim 1, it is characterised in that: step (3) fine grinding ore pulp is done
The solid-to-liquid ratio kg:L of base and Weak-acid leaching liquid A are (0.40 ~ 0.50): (5.5 ~ 7.5).
6. rich germanium zinc oxide fumes leaching method according to claim 1, it is characterised in that: step (4) neutralizes the dry of underflow
The solid-to-liquid ratio kg:kg:L of base, the butt of low sour underflow and zinc hydrometallurgy electrolysis waste solution is (0.20 ~ 0.30): (0.35 ~ 0.45):
(5.5~7.5)。
7. rich germanium zinc oxide fumes leaching method according to claim 1, it is characterised in that: filter-press residues is dry in step (4)
The solid-to-liquid ratio kg:L of base and water is (0.55 ~ 0.65): (1.5 ~ 2.5).
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| CN115323179A (en) * | 2022-08-22 | 2022-11-11 | 昆明理工大学 | Method for inhibiting formation of iron silicon germanium colloidal precipitate during deacidification of germanium-containing leachate with high acid content by using ultrasound |
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| CN115216651A (en) * | 2022-09-06 | 2022-10-21 | 昆明冶金研究院有限公司 | Method for efficiently recycling zinc and germanium in zinc oxide smoke dust |
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