CN114182102A - Method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate - Google Patents
Method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate Download PDFInfo
- Publication number
- CN114182102A CN114182102A CN202111329300.0A CN202111329300A CN114182102A CN 114182102 A CN114182102 A CN 114182102A CN 202111329300 A CN202111329300 A CN 202111329300A CN 114182102 A CN114182102 A CN 114182102A
- Authority
- CN
- China
- Prior art keywords
- germanium
- leaching
- zinc oxide
- hydrazine sulfate
- oxide smoke
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 101
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002386 leaching Methods 0.000 title claims abstract description 97
- 239000000779 smoke Substances 0.000 title claims abstract description 52
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 52
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910000377 hydrazine sulfate Inorganic materials 0.000 title claims abstract description 35
- 239000012493 hydrazine sulfate Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000428 dust Substances 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001308 Zinc ferrite Inorganic materials 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 230000009471 action Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- SCCCLDWUZODEKG-UHFFFAOYSA-N germanide Chemical compound [GeH3-] SCCCLDWUZODEKG-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
-
- 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
-
- 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 invention relates to a method for reducing and leaching germanium in zinc oxide smoke dust containing germanium by hydrazine sulfate, belonging to the technical field of hydrometallurgy, the invention utilizes hydrazine sulfate as a reducing agent to leach germanium in the zinc oxide smoke dust, and can obviously improve the leaching rate of germanium by controlling the acidity, liquid-solid ratio and the using amount of the reducing agent in the leaching process, the leaching is completed under the ultrasonic synergistic effect, the leaching rate is further improved, and the leaching time is further shortened; the method has the advantages of high leaching rate and less leaching residue, obviously overcomes the defect of low leaching rate caused by the fact that tetravalent germanium replaces ferric ions and enters crystal lattices of zinc ferrite, is harmless to other valuable metals extracted by a subsequent process, and finally achieves the leaching rate of germanium of about 96%. Has better environmental protection benefit and economic benefit.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate.
Background
Germanium is an important rare metal and is widely used in the fields of aerospace, national defense and military industry, electronics, semiconductors and the like, however, with the rapid development of science and technology, the global demand for germanium is increasing day by day, and germanium metal and compounds thereof have extremely important significance for the development of various aspects of the country. Germanium is mainly associated in sulfide ores and brown coal ores of metals such as Zn, Pb, Cu and the like, and an independent germanium ore deposit is not found in nature at present. Meanwhile, germanium is often embedded with other metals tightly due to properties of germanite, sulfur and iron, and the like, so that the germanium is difficult to separate.
At present, the main raw materials for extracting germanium in China comprise byproducts generated in the smelting process of metals such as lead, zinc and the like and flue dust generated by combustion of lignite, but because the content of germanium in the germanium-containing materials is too low, the germanium is often required to be enriched by adopting a certain method and then concentrated, separated and extracted. In the zinc smelting process, a fuming method is usually adopted to enrich germanium in zinc oxide smoke dust, and the content of germanium in the zinc oxide smoke dust can reach more than 500 g/t. The germanium in the zinc oxide smoke is recovered, at present, domestic and foreign enterprises generally adopt reducing agents such as sodium sulfite and sulfur dioxide to reduce and leach germanium in germanium-containing zinc oxide smoke, the reducing agents are used, the germanium can be effectively leached only under high acid (the acidity is about 180 g/L) or by adopting multi-stage leaching, the leaching time is long, the leaching temperature requirement is high (about 80 ℃), the leaching rate is low, generally 60-80%, in addition, the reducing agents not only can generate a large amount of sulfur-containing waste gas, but also have large slag production amount, so that the valuable metal loss is serious, and the environmental protection pressure of the enterprises is increased.
In addition, after the zinc oxide smoke dust is subjected to reduction leaching, the leaching solution is sent to a subsequent electrodeposition process to recover zinc in the leaching solution, the electrodeposition process needs to control the electrodeposition solution to a certain acidity, and the final acid pH of the acid leaching solution is higher due to the fact that high acid is needed during leaching of the current acid leaching solution of the zinc oxide smoke dust, the electrodeposition can be carried out only after alkali treatment is needed before electrodeposition, in the field of industrial production, extra cost is generated and material consumption and loss are increased when one process is added, which is obviously undesirable for enterprises.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for reducing and leaching germanium in zinc oxide smoke dust containing germanium by hydrazine sulfate.
In order to realize the purpose, the invention is realized by the following technical scheme:
the method for reducing and leaching germanium in germanium-containing zinc oxide smoke by using hydrazine sulfate is characterized in that the hydrazine sulfate is used as a reducing agent for germanium leaching, and the leaching method comprises the following steps:
adding sulfuric acid solution and hydrazine sulfate reducing agent into zinc oxide smoke dust to leach germanium, wherein,
the usage amount of hydrazine sulfate is: n (iron) n (hydrazine sulfate) is 1-6: 1;
the leaching acidity is: 100-180 g/L;
the liquid-solid ratio is: 4-8 ml/g.
Further, the leaching temperature is 50-90 ℃.
Further, the zinc oxide smoke dust is dried and screened, and then germanium is leached, wherein the screening mesh number is 50-200 meshes.
Further, germanium leaching is completed under the coordination of ultrasound.
Furthermore, the power of the ultrasonic wave is 0.3-4.0W/mL.
Further, the zinc oxide smoke dust is dried under vacuum condition.
The invention has the beneficial effects that:
according to the method, the hydrazine sulfate is used as a reducing agent to leach germanium in the zinc oxide smoke dust, so that compared with other methods, the initial acidity is reduced, the leaching rate is improved, and the production cost is reduced; in addition, only nitrogen is generated in the leaching process, and the influence on the subsequent electrodeposition process cannot be generated.
The invention also obviously overcomes the defect that tetravalent germanium replaces ferric ions and enters the crystal lattice of zinc ferrite, not only has high leaching rate, but also reduces the waste residue production amount by about 10 percent in the whole leaching process. In addition, under the ultrasonic synergistic effect, the leaching time is shortened, the leaching rate is further improved, and the highest leaching rate of germanium can reach about 96%.
Compared with the existing germanium leaching technology of zinc oxide smoke dust, the method has the characteristics of simple process, no waste gas, small waste residue rate, short germanium leaching time and high leaching rate, and has better environmental protection benefit and economic benefit.
Drawings
FIG. 1 is an XRD pattern of zinc oxide soot in an example of the present invention;
FIG. 2 is an XRD pattern of the leached slag of example 1 of the present invention;
FIG. 3 is an FE-SEM image (at different magnifications) of zinc oxide soot in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
The method for reducing and leaching germanium in the zinc oxide smoke dust containing germanium by using hydrazine sulfate comprises the following steps of drying the zinc oxide smoke dust, screening by using a 50-200-mesh sieve, and leaching germanium, wherein the leaching method comprises the following steps:
adding a sulfuric acid solution and a hydrazine sulfate reducing agent into zinc oxide smoke dust for germanium leaching, wherein: the usage amount of hydrazine sulfate is: n (iron) n (hydrazine sulfate) is 1-6: 1 (molar ratio); the leaching acidity is: 100-180 g/L; the liquid-solid ratio is: 4-8 ml/g; the leaching temperature is 50-90 ℃.
By adding hydrazine sulfate, zinc ferrite and other objects which are easy to embed germanium are reacted under the action of sulfuric acid, so that germanium compounds in smoke dust are exposed, and compared with reducing agents such as sulfur dioxide and sodium sulfite, hydrazine sulfate can obviously overcome the defect that trivalent iron ions are replaced by tetravalent germanium and enter crystal lattices of zinc ferrite to cause low leaching rate.
The specific reaction is as follows:
MeO·Fe2O3+8H+→Me2++2Fe3++4H2O
N2H5 ++Fe3+→NH4 ++1/2N2↑+H++Fe2+
and ultrasonic synergistic leaching of 0.3-4.0W/mL is adopted, so that the reaction of sulfuric acid and compounds in smoke dust can be accelerated, and the leaching rate of germanium is as high as about 96%.
In the examples of the present invention, phase analysis was performed using an X-ray diffractometer (XRD) (D8 ADVANCE) with Cu — K α as an X-ray source, λ 0.15416nm, voltage ≤ 40KV, and current ≤ 40 mA; the morphology of the sample is observed by field emission scanning electron microscopy (FE-SEM) (JEOL JSM-7800F); sample particle size was measured by a laser particle sizer (Mastersizer 3000).
All the embodiments of the invention use the same batch of germanium-containing zinc oxide smoke dust, and the main chemistry is as follows:
TABLE 1 Zinc oxide Smoke dust principal Components TABLE
Composition (I) | Zn | Pb | S | Fe | Si | As | K | Cd | Al | Ca | Cl | Ge(g/t) |
Content% | 54.72 | 14.39 | 3.78 | 1.79 | 0.71 | 0.59 | 0.44 | 0.42 | 0.42 | 0.19 | 0.10 | 510.10 |
Example 1
Weighing 40g of zinc oxide smoke dust containing germanium and sieved by 200 meshes after drying, placing the zinc oxide smoke dust containing germanium into a reactor, then adding a sulfuric acid solution into the zinc oxide smoke dust, controlling the acidity of a reaction solution to be 140g/L and the liquid-solid ratio to be 8ml/g, and according to the detection result of iron in the zinc oxide smoke dust, according to the following formula that n (iron) n (hydrazine sulfate) ═ 3:1 adding reducing agent hydrazine sulfate. Stirring and leaching for 60min under the action of 1.07W/mL ultrasonic waves at the constant temperature of 60 ℃. And filtering after leaching, drying the filter residue at 60 ℃ for 15h to obtain 14.68g of dry-base filter residue, and detecting to obtain the filtrate with the germanium content of 64.4mg/L and the germanium leaching rate of 95.97%.
The XRD pattern of the zinc oxide smoke dust containing germanium after being dried in the embodiment is shown in figure 1, and the FE-SEM pattern is shown in figure 3; the XRD pattern of the leached dry residue is shown in figure 2.
Comparative example 1
The comparative example is the same as example 1 except that ultrasonic waves are not used, and the filter residue is dried for 15 hours at 60 ℃ to obtain 15.57g of dry-base filter residue, and the content of germanium in the filtrate is detected to be 61.90mg/L, and the leaching rate of germanium is 91.03%. Without the use of ultrasonic waves, the leaching rate of germanium is reduced.
In order to verify the influence degree of the ultrasonic wave-free leaching, the leaching time is only prolonged by using the same experimental raw materials and conditions, and the leaching rate is proved to be maximum when the leaching time is prolonged to 120min, and the leaching rate of the germanium is 91.47%.
Example 2
Weighing 40g of zinc oxide smoke dust containing germanium and sieved by 200 meshes after drying, placing the zinc oxide smoke dust into a reactor, then adding a sulfuric acid solution into the zinc oxide smoke dust, controlling the acidity of a reaction solution to be 140g/L and the liquid-solid ratio to be 4-8ml/g, and adding a reducing agent of which n (iron) and n (hydrazine sulfate) are 3: 1. Stirring at constant temperature of 60 ℃, controlling the rotating speed at 200-500r/min, and leaching for 60min under the action of ultrasonic waves. And then filtering, drying the filter residue at 60 ℃ for 15h, weighing and detecting the filtrate and the filter residue, and calculating the germanium leaching rate.
TABLE 2 influence of liquid-solid ratio on germanium leaching rate
Liquid-solid ratio (ml/g) | Amount of filtrate (mL) | Germanium content of filtrate (mg/L) | Amount of residue (g) | Germanium leaching rate/%) |
4 | 143 | 43.2 | 19.79 | 30.28 |
5 | 180 | 66.7 | 17.89 | 58.85 |
6 | 224 | 81.9 | 15.17 | 89.93 |
7 | 270 | 71.49 | 14.82 | 94.62 |
8 | 304 | 64.4 | 14.68 | 95.97 |
In the leaching process, the liquid-solid ratio has a crucial influence on the leaching rate of germanium, when the liquid-solid ratio is 6-8 mL/g, the leaching rate of germanium is higher, and when the liquid-solid ratio is lower than 6mL/g, the leaching rate of germanium is low, mainly because the amount of added sulfuric acid is small, so that the reaction cannot be completely carried out. In addition, when the liquid-solid ratio is lower than 6mL/g, ferric iron in the solution can be hydrolyzed and coprecipitated, and a part of germanide is taken away, so that the leaching rate is low. On the other hand, when the leaching rate is higher than 7mL/g, the leaching rate of germanium does not change much. Therefore, the liquid/solid ratio is preferably 7mL/g from the viewpoint of economy.
Example 3
Weighing 40g of zinc oxide smoke dust containing germanium and sieved by 200 meshes after drying, placing the zinc oxide smoke dust containing germanium in a reactor, then adding a sulfuric acid solution into the zinc oxide smoke dust, controlling the acidity of a reaction solution to be 100-180g/L and the liquid-solid ratio to be 7ml/g, and adding n (iron) and n (hydrazine sulfate) to be 1: 1. Under the action of a constant-temperature magnetic stirring water bath, the rotating speed is controlled to be 100-500r/min, the leaching temperature is 70 ℃, and the leaching time is 30min under the action of ultrasonic waves. Then filtered and the residue dried at 60 ℃ for 15 h.
TABLE 3 influence of acidity on germanium leaching rate
Acidity (g/L) | Amount of filtrate (mL) | Germanium content of filtrate (mg/L) | Germanium leaching rate/%) |
100 | 266 | 46.04 | 60.03 |
120 | 269 | 64.93 | 85.62 |
140 | 269 | 69.29 | 91.37 |
160 | 270 | 69.50 | 91.99 |
180 | 268 | 70.22 | 92.25 |
Comparative example 2
Controlling the reaction acidity to be 180g/L, using sodium sulfite to replace hydrazine sulfate under the same other conditions as in example 3, leaching to obtain 268mL of filtrate, and detecting to obtain 60.59mL/g of germanium content in the filtrate and 79.6% of germanium leaching rate.
Comparative example 3
The other conditions are the same as the example 3, sodium sulfite is used for replacing hydrazine sulfate, the leaching acidity is controlled to be 180g/L, the leaching time is prolonged to 60min, 266mL of filtrate is obtained, the content of germanium in the filtrate is detected to be 64.13mL/g, and the leaching rate of germanium is 83.62%.
Comparative example 4
The other conditions are the same as the example 3, sodium sulfite is used for replacing hydrazine sulfate, the leaching acidity is controlled to be 180g/L, the leaching temperature is increased to 80 ℃, the leaching time is prolonged to 60min, 263mL of filtrate is obtained, the content of germanium in the filtrate is 65.27mL/g through detection, and the leaching rate of germanium is 84.15%.
Example 4
Weighing 40g of zinc oxide smoke dust containing germanium and screened by a 100-mesh sieve after drying, placing the zinc oxide smoke dust into a reactor, then adding a sulfuric acid solution into the zinc oxide smoke dust, controlling the acidity of a reaction solution to be 160g/L and the liquid-solid ratio to be 6ml/g, and adding n (iron): n (hydrazine sulfate) ═ 1: 1. Stirring at constant temperature of 90 ℃, controlling the rotating speed to be 100-500r/min, and leaching for 60min under the action of ultrasonic waves. The leaching rate of germanium is 91.25%.
Example 5
Weighing 40g of zinc oxide smoke dust containing germanium and sieved by 200 meshes after drying, placing the zinc oxide smoke dust containing germanium in a reactor, adding a sulfuric acid solution into the zinc oxide smoke dust, controlling the acidity of a reaction solution to be 140g/L and the liquid-solid ratio to be 7ml/g, and adding n (iron): n (hydrazine sulfate) ═ 2: 1. Stirring at a constant temperature of 70 ℃, controlling the rotating speed to be 100-500r/min, and leaching for 60min under the action of ultrasonic waves. Then filtering, drying the filter residue under vacuum at 60 ℃, detecting the content of germanium in the filtrate and the filter residue, and calculating the leaching rate of the obtained germanium to be 94.24%.
Example 6
Weighing 40g of zinc oxide smoke dust containing germanium and sieved by 200 meshes after drying, placing the zinc oxide smoke dust into a reactor, then adding a sulfuric acid solution into the zinc oxide smoke dust, controlling the acidity of a reaction solution to be 120g/L and the liquid-solid ratio to be 8ml/g, and adding a reducing agent of which n (iron) and n (hydrazine sulfate) are 4: 1. Stirring at constant temperature of 80 ℃, controlling the rotating speed at 100-. And then filtering, drying the filter residue at 60 ℃ for 15h in vacuum, detecting the content of germanium in the filtrate and the filter residue, and calculating to obtain the leaching rate of the germanium to be 92.68%.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (5)
1. A method for reducing and leaching germanium in germanium-containing zinc oxide smoke dust by hydrazine sulfate is characterized by comprising the following steps:
adding sulfuric acid solution and hydrazine sulfate reducing agent into zinc oxide smoke dust to leach germanium, wherein,
the usage amount of hydrazine sulfate is: n (iron) = 1-6: 1;
the leaching acidity is: 100-180 g/L;
the liquid-solid ratio is: 4-8 mL/g.
2. The method for reducing and leaching germanium in zinc oxide smoke containing germanium by using hydrazine sulfate according to claim 1, wherein the method comprises the following steps: the leaching temperature is 50-90 ℃.
3. The method for reducing and leaching germanium in zinc oxide smoke containing germanium by using hydrazine sulfate according to claim 1, wherein the method comprises the following steps: and drying and screening the zinc oxide smoke dust, and then leaching germanium, wherein the screening mesh number is 50-200 meshes.
4. A method for reducing and leaching germanium in zinc oxide smoke containing germanium by using hydrazine sulfate according to any one of claims 1 to 3, characterized in that: germanium leaching is completed under the coordination of ultrasound.
5. The method for reducing and leaching germanium in zinc oxide smoke containing germanium by using hydrazine sulfate according to claim 4, wherein the method comprises the following steps: the power of the ultrasonic wave is 0.3-4.0W/mL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111329300.0A CN114182102A (en) | 2021-11-10 | 2021-11-10 | Method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111329300.0A CN114182102A (en) | 2021-11-10 | 2021-11-10 | Method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114182102A true CN114182102A (en) | 2022-03-15 |
Family
ID=80539900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111329300.0A Pending CN114182102A (en) | 2021-11-10 | 2021-11-10 | Method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114182102A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN115537584A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for strengthening tannin germanium precipitation through ultrasonic and tannic acid modification |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104561565A (en) * | 2015-01-29 | 2015-04-29 | 中南大学 | Method for reduction leaching of cadmium from zinc smelting neutral leaching residues |
CN108715938A (en) * | 2018-07-16 | 2018-10-30 | 四环锌锗科技股份有限公司 | A kind of technique improving the electric Zn system germanium rate of recovery |
-
2021
- 2021-11-10 CN CN202111329300.0A patent/CN114182102A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104561565A (en) * | 2015-01-29 | 2015-04-29 | 中南大学 | Method for reduction leaching of cadmium from zinc smelting neutral leaching residues |
CN108715938A (en) * | 2018-07-16 | 2018-10-30 | 四环锌锗科技股份有限公司 | A kind of technique improving the electric Zn system germanium rate of recovery |
Non-Patent Citations (3)
Title |
---|
宁继来;郑永兴;胡盘金;庞杰;: "锌冶炼渣选冶联合技术研究进展", 《矿冶》, no. 03, pages 18 - 24 * |
辛椿福 等: "含锗氧化锌烟尘中有价金属回收利用研究进展", 《有色金属工程》, vol. 11, no. 6, pages 66 - 74 * |
闵小波 等: "锌冶炼中浸渣锌还原浸出行为研究", 《有色金属科学与工程》, vol. 6, no. 5, pages 1 - 6 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN115537584A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for strengthening tannin germanium precipitation through ultrasonic and tannic acid modification |
CN115537584B (en) * | 2022-11-29 | 2023-03-10 | 昆明理工大学 | Method for reinforcing tannin germanium precipitation through ultrasonic and tannic acid modification |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10081851B2 (en) | Method for recovering high-purity scandium | |
JP3740491B1 (en) | Fluorine adsorption / desorption agent capable of adsorbing and desorbing fluorine in electrolyte in zinc electrolytic smelting, and fluorine removal method using the fluorine adsorption / desorption agent | |
CN114182102A (en) | Method for reducing and leaching germanium in germanium-containing zinc oxide smoke by hydrazine sulfate | |
JP2015227509A (en) | Recovery method of scandium | |
CN103526021A (en) | Cleansing and cobalt-removing method for zinc smelting leachate and scavenging agent used therein | |
CN110284004B (en) | Method for synergistically recycling copper slag and sodium sulfate waste slag | |
CN112430733A (en) | Method for treating laterite-nickel ore | |
CN108502915A (en) | A method of nano zine oxide is prepared with high zinc dedusting ash | |
CN103805785A (en) | Method for recovering gallium from fly ash | |
CN103074496B (en) | Method for separating and purifying magnesium dioxide from anode mud | |
EP3342887A1 (en) | Scandium oxide manufacturing method | |
CN112410555A (en) | Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue | |
CN116676498A (en) | Method for auxiliary leaching germanium in high-silicon germanium-containing zinc oxide smoke dust | |
CN113403486A (en) | Process for removing iron from nickel sulfide concentrate leachate by goethite method | |
CN110643808B (en) | Method for extracting tungsten from low-grade wolframite | |
JPH06212304A (en) | Method for smelting zinc | |
CN107233884B (en) | Ferromagnetic catalyst for catalyzing hydrolysis and precipitation of trivalent iron, and preparation method and application thereof | |
CN113122735B (en) | Alkali-process zinc powder combined smelting method | |
CN111411224B (en) | Beneficiation method for comprehensively recovering and combining silver and copper from low-grade manganese-containing ore | |
CN104774979B (en) | A kind of method being prepared chromium sulfate basic tanning extracts by chromite sulphuric leachate | |
CN113293314A (en) | Method for leaching and separating bismuth from blast furnace gas ash or/and mud | |
CN114015896B (en) | Method for extracting metallic nickel from nickel-iron alloy | |
CN108728643B (en) | Method for separating antimony and iron by extraction-water decomposition in antimony-iron mixed solution | |
CN113388732A (en) | Beneficiation method for comprehensively recovering iron and gold from iron and gold ore | |
JP4806820B2 (en) | Method for indium sulfide from indium-containing material and method for recovering indium |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |