CN112028113A - Method for recovering zinc oxide powder in zinc hydrometallurgy process - Google Patents
Method for recovering zinc oxide powder in zinc hydrometallurgy process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011701 zinc Substances 0.000 title claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 72
- 238000001914 filtration Methods 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 32
- 150000007524 organic acids Chemical class 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 11
- 239000011976 maleic acid Substances 0.000 claims description 11
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011667 zinc carbonate Substances 0.000 description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 description 3
- 235000004416 zinc carbonate Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention belongs to the field of zinc oxide powder recovery, and particularly discloses a method for recovering zinc oxide powder in a zinc hydrometallurgy process. The process has the advantages of few steps, mild reaction conditions, simple equipment requirement, energy conservation and environmental protection, and the prepared zinc oxide powder has high purity, changes waste into valuable and is suitable for being widely used by zinc hydrometallurgy enterprises.
Description
Technical Field
The invention belongs to the field of zinc oxide powder recovery, and particularly discloses a method for recovering zinc oxide powder in a zinc hydrometallurgy process.
Background
Zinc oxide is an oxide of zinc, is insoluble in water, is soluble in acid and strong base, is a common chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint coatings, ointments, adhesives, foods, batteries, flame retardants and the like. The zinc hydrometallurgy of zinc refers to a process of dissolving zinc in zinc calcine or other zinc sulfide materials and zinc in zinc sulfide concentrate in water solution and extracting metallic zinc or zinc compounds from the zinc calcine or other zinc sulfide materials and zinc sulfide concentrate, and is a main method of modern zinc smelting. Consists of three large links of zinc leaching, purification from zinc solution and zinc electrolytic deposition. The zinc hydrometallurgy mainly comprises the working procedures of roasting, leaching, leachate purification, electrodeposition and the like. At present, in the zinc hydrometallurgy process, the zinc content of calcine is often more than half, leaches through sulphuric acid, and the most gets into solution with zinc sulfate for electrolytic preparation zinc, but the zinc content in its waste residue that leaches still often exceeds 20%, abandons not to be very pity, and the tradition uses the rotary kiln to volatilize, retrieves zinc, lead and some rare metal wherein, but has the energy consumption shortcoming big, inefficiency.
Disclosure of Invention
Based on the method, the method for recovering the zinc oxide powder in the zinc hydrometallurgy process provided by the invention has the advantages of few steps, mild reaction conditions, simple requirements on equipment, energy conservation and environmental protection.
The technical scheme of the invention is as follows:
a method for recovering zinc oxide powder in a zinc hydrometallurgy process is characterized by comprising the following steps:
1) filtering the waste residue obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 20-100 mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting pH to 2.5-3.5; heating to 60-80 ℃, and stirring for reaction for 4-8 h;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to be 4.5-5.5, and stirring for reaction for 1-2 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the adding amount is that the concentration of the final solution potassium permanganate solution is 0.01-0.1 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.05-0.2 mol/L;
5) filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 70-90 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 9.5-11, and adding supersaturated carbonate to react for 30-60 min;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and sending the precipitate into a vacuum drying box for drying at the temperature of 120-;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 400-450 ℃ for 6-8 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
Further, in the above method for recovering zinc oxide powder in the zinc hydrometallurgy process, in step 1, the acid is concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the acid to the concentrated nitric acid is 1: 2.
further, in the above method for recovering zinc oxide powder in the zinc hydrometallurgy process, in step 4, the organic acid is one or more of oxalic acid, maleic acid, tartaric acid, and sulfamic acid.
Further, in the method for recovering the zinc oxide powder in the zinc hydrometallurgy process, the organic acid is a mixed acid of maleic acid and sulfamic acid, and the molar ratio of the maleic acid to the sulfamic acid is 3: 1.
Further, in the above method for recovering zinc oxide powder in the zinc hydrometallurgy process, in step 5, the alkali is sodium hydroxide.
Further, the method for recovering zinc oxide powder in the zinc hydrometallurgy process comprises the following steps
1) Filtering waste residues obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 50-mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting the pH value to 3.0; heating to 70 ℃, and stirring for reaction for 6 hours;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to 5, and stirring for reaction for 1.5 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the addition amount is that the concentration of the final solution potassium permanganate solution is 0.05 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.1 mol/L;
5) filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 80 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 10, and adding supersaturated carbonate to react for 45 min;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and drying the precipitate in a vacuum drying oven at 130 ℃;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 420 ℃ for 7 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
Compared with the prior art, the invention has the beneficial effects that:
after the zinc oxide powder is subjected to two-stage acid leaching, the supernatant is subjected to iron removal, germanium is precipitated by organic acid, germanium residue and solution are separated, zinc carbonate is precipitated, rapid separation of residue and liquid is realized, elements such as zinc, iron and germanium in the solution are thoroughly separated by accurately adjusting PH, high-purity zinc carbonate is prepared, and the zinc carbonate is calcined to generate high-purity zinc oxide powder.
Detailed Description
A method for recovering zinc oxide powder in a zinc hydrometallurgy process comprises the following steps:
1) filtering the waste residue obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 20-100 mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting pH to 2.5-3.5; heating to 60-80 ℃, and stirring for reaction for 4-8 h; the acid is concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the acid to the concentrated nitric acid is 1: 2;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to be 4.5-5.5, and stirring for reaction for 1-2 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the adding amount is that the concentration of the final solution potassium permanganate solution is 0.01-0.1 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.05-0.2 mol/L; the organic acid is one or more of oxalic acid, maleic acid, tartaric acid and sulfamic acid; further, the organic acid is a mixed acid of maleic acid and sulfamic acid, and the molar ratio of the maleic acid to the sulfamic acid is 3: 1.
5) Filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 70-90 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 9.5-11, and adding supersaturated carbonate to react for 30-60 min; preferably, the alkali is sodium hydroxide, and the carbonate is sodium carbonate or ammonium carbonate, more preferably ammonium carbonate.
6) Filtering the stirring liquid obtained in the step 5, washing the precipitate, and sending the precipitate into a vacuum drying box for drying at the temperature of 120-;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 400-450 ℃ for 6-8 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The invention provides a method for recovering zinc oxide powder in a zinc hydrometallurgy process, which comprises the following steps:
1) filtering waste residues obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 20-mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting the pH value to 2.5; heating to 60 ℃, and stirring for reaction for 4 hours; the acid is concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the acid to the concentrated nitric acid is 1: 2;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to 4.5, and stirring for reaction for 1 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the addition amount is that the concentration of the final solution potassium permanganate solution is 0.01 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.05 mol/L; the organic acid is tartaric acid;
5) filtering and deslagging the stirring solution obtained in the step 4, heating and stirring at 70 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 9.5, and adding supersaturated carbonate to react for 30 ℃; the alkali is sodium hydroxide, and the carbonate is sodium carbonate;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and drying the precipitate in a vacuum drying oven at 120 ℃;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 400 ℃ for 6 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
Example 2
The invention provides a method for recovering zinc oxide powder in a zinc hydrometallurgy process, which comprises the following steps:
1) filtering waste residues obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 60-mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting the pH value to 3.0; heating to 70 ℃, and stirring for reaction for 6 hours; the acid is concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the acid to the concentrated nitric acid is 1: 2;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to 5, and stirring for reaction for 1.5 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the addition amount is that the concentration of the final solution potassium permanganate solution is 0.05 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.1 mol/L; the organic acid is a mixed acid of maleic acid and sulfamic acid, and the molar ratio of the maleic acid to the sulfamic acid is 3: 1;
5) filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 80 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 10, and adding supersaturated carbonate to react for 45 min; the alkali is sodium hydroxide, and the carbonate is ammonium carbonate;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and drying the precipitate in a vacuum drying oven at 130 ℃;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 420 ℃ for 7 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
Example 3
The invention provides a method for recovering zinc oxide powder in a zinc hydrometallurgy process, which comprises the following steps:
1) filtering waste residues obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 100-mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting the pH value to 3.5; heating to 80 ℃, and stirring for reaction for 8 hours; the acid is concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the acid to the concentrated nitric acid is 1: 2;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to 5.5, and stirring for reaction for 2 hours;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the adding amount is that the concentration of the final solution potassium permanganate solution is 0.1 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.2 mol/L; the organic acid is oxalic acid;
5) filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 90 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 11, and adding supersaturated carbonate to react for 60 min; the alkali is sodium hydroxide, and the carbonate is sodium carbonate;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and drying the precipitate in a vacuum drying oven at 140 ℃;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 450 ℃ for 8 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
Test example
Three zinc oxide powders prepared by the recovery methods of examples 1, 2, 3, etc. were subjected to composition detection, and the test results are shown in table 1.
TABLE 1 component detection
| Example 1 | Example 2 | Example 3 | |
| Zinc oxide% | 98.2 | 99.2 | 97.8 |
| Iron% | 0.4 | 0.3 | 0.5 |
| Germanium% | 0.02 | 0.01 | 0.03 |
| Chromium% | 0.12 | 0.09 | 0.11 |
| Cobalt% | 0.03 | 0.02 | 0.04 |
According to the data in the table 1, the recovery method has the advantages of few steps, mild reaction conditions, simple equipment requirements, energy conservation and environmental protection, and the prepared zinc oxide powder has high purity and few impurities and is suitable for being widely used by zinc hydrometallurgy enterprises.
The foregoing is only a preferred embodiment of the present invention. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for recovering zinc oxide powder in a zinc hydrometallurgy process is characterized by comprising the following steps:
1) filtering the waste residue obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 20-100 mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting pH to 2.5-3.5; heating to 60-80 ℃, and stirring for reaction for 4-8 h;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to be 4.5-5.5, and stirring for reaction for 1-2 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the adding amount is that the concentration of the final solution potassium permanganate solution is 0.01-0.1 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.05-0.2 mol/L;
5) filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 70-90 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 9.5-11, and adding supersaturated carbonate to react for 30-60 min;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and sending the precipitate into a vacuum drying box for drying at the temperature of 120-;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 400-450 ℃ for 6-8 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
2. The method for recovering zinc oxide powder in the zinc hydrometallurgy process of claim 1, wherein in the step 1, the acid is concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 2.
3. the method for recovering zinc oxide powder in the zinc hydrometallurgy process of claim 1, wherein in the step 4, the organic acid is one or more of oxalic acid, maleic acid, tartaric acid and sulfamic acid.
4. The method as claimed in claim 3, wherein the organic acid is a mixed acid of maleic acid and sulfamic acid, and the molar ratio of the maleic acid to the sulfamic acid is 3: 1.
5. The method for recovering zinc oxide powder in a zinc hydrometallurgy process of claim 1, wherein in step 5, the alkali is sodium hydroxide.
6. The method for recovering zinc oxide powder in a zinc hydrometallurgy process according to claim 1, wherein in step 5, the carbonate is sodium carbonate or ammonium carbonate.
7. The method for recovering zinc oxide powder in the zinc hydrometallurgy process of claim 1, which is characterized by comprising the following steps:
1) filtering waste residues obtained after zinc hydrometallurgy, completely drying, putting into a ball mill, grinding into powder, sieving with a 50-mesh sieve, putting into a stirring tank, adding deionized water, adding acid, and adjusting the pH value to 3.0; heating to 70 ℃, and stirring for reaction for 6 hours;
2) filtering the stirring liquid obtained in the step 1; adding a proper amount of deionized water, adjusting the pH value to 5, and stirring for reaction for 1.5 h;
3) adding potassium permanganate into the stirring solution obtained in the step 2 to remove iron, wherein the addition amount is that the concentration of the final solution potassium permanganate solution is 0.05 mol/L;
4) filtering the stirring liquid obtained in the step (3) to remove residues, and adding organic acid to remove germanium, wherein the addition amount is that the final organic acid concentration is 0.1 mol/L;
5) filtering the stirring liquid obtained in the step (4) to remove residues, heating and stirring at 80 ℃, performing ultrasonic treatment, adding alkali to adjust the pH value to 10, and adding supersaturated carbonate to react for 45 min;
6) filtering the stirring liquid obtained in the step 5, washing the precipitate, and drying the precipitate in a vacuum drying oven at 130 ℃;
7) putting the dried precipitate into a muffle furnace for calcination decomposition at the temperature of 420 ℃ for 7 h; and naturally cooling after the calcination is finished to obtain the zinc oxide powder.
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| CN106830051A (en) * | 2017-01-19 | 2017-06-13 | 红河学院 | A kind of method for preparing nanometer Zinc oxide powder as raw material with industrial zinc oxide |
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