CN109022820B - Method for producing zinc oxide by using leaching residues of electrolytic zinc acid method - Google Patents
Method for producing zinc oxide by using leaching residues of electrolytic zinc acid method Download PDFInfo
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- CN109022820B CN109022820B CN201810817428.3A CN201810817428A CN109022820B CN 109022820 B CN109022820 B CN 109022820B CN 201810817428 A CN201810817428 A CN 201810817428A CN 109022820 B CN109022820 B CN 109022820B
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- Prior art keywords
- leaching
- calcium
- zincate
- zinc
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000002386 leaching Methods 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000011701 zinc Substances 0.000 title claims description 85
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 74
- 229910052725 zinc Inorganic materials 0.000 title claims description 73
- 239000002253 acid Substances 0.000 title claims description 18
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 80
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011575 calcium Substances 0.000 claims abstract description 46
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 43
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 14
- 230000023556 desulfurization Effects 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 39
- 239000000920 calcium hydroxide Substances 0.000 claims description 39
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 39
- 239000000706 filtrate Substances 0.000 claims description 28
- 239000000292 calcium oxide Substances 0.000 claims description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000002500 ions Chemical class 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 235000011132 calcium sulphate Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229940007718 zinc hydroxide Drugs 0.000 description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052925 anhydrite Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- FWABRVJYGBOLEM-UHFFFAOYSA-N diazanium;azane;carbonate Chemical compound N.[NH4+].[NH4+].[O-]C([O-])=O FWABRVJYGBOLEM-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SRONXGSXMGLHAE-UHFFFAOYSA-N C(O)(O)=O.N[Zn]N Chemical compound C(O)(O)=O.N[Zn]N SRONXGSXMGLHAE-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 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
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- QGQBPUNOAXJRIZ-UHFFFAOYSA-M [NH4+].S(=O)(=O)([O-])[O-].N.[Zn+] Chemical compound [NH4+].S(=O)(=O)([O-])[O-].N.[Zn+] QGQBPUNOAXJRIZ-UHFFFAOYSA-M 0.000 description 1
- MUHUIJPSGRCRFX-UHFFFAOYSA-M [Zn+].C([O-])([O-])=O.[NH4+] Chemical compound [Zn+].C([O-])([O-])=O.[NH4+] MUHUIJPSGRCRFX-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 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
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- HYJPZWOFVGWLCA-UHFFFAOYSA-N diazanium zinc carbonate Chemical compound [Zn].[NH4+].C([O-])([O-])=O.[NH4+] HYJPZWOFVGWLCA-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011451 fired brick Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010956 selective crystallization Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- C22B19/34—Obtaining zinc oxide
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present disclosure relates to a method for producing zinc oxide by using leaching residue of an electrolytic zincate method, which comprises a leaching step, an optional purification step, a desulfurization step, a calcium zincate synthesis step, an optional rinsing step, a calcination step and a calcium-zinc separation step. The method disclosed by the invention realizes secondary utilization of leaching residues while solving the environmental protection problem, realizes resource utilization while solving the pollution of various heavy metals, does not need ammonia distillation, is simple and easy, and also greatly reduces the energy consumption of the process.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of resources and comprehensive application of new materials, relates to environment-friendly treatment and resource utilization of leaching residues of an electrolytic zincic acid method, and particularly relates to a method for producing zinc oxide by using the leaching residues of the electrolytic zincic acid method.
Background
The leaching slag of the electrolytic zincate method is the most main pollutant in the electrolytic zinc industry, and belongs to the leaching slag generated by the conventional leaching method in the lead-zinc smelting process and the sulfur slag (leaching slag) generated by the normal pressure oxygen leaching and the pressure oxygen leaching in the national hazardous waste catalogue. The treatment and resource utilization of the leaching residue by the electrolytic zincate method are problems which need to be solved urgently. Meanwhile, the production and consumption of zinc in China are at the top of the world, domestic zinc resources cannot meet the production, and a large amount of zinc raw materials need to be imported every year. The method is developed to realize the high-efficiency resource utilization of the zinc in the leaching residue of the electrolytic zincic acid method, and has important significance for solving the environmental protection pressure and relieving the domestic zinc raw material supply problem.
Calcium zincate has a wide range of uses. The application of calcium zincate to the negative electrode material of the alkaline secondary zinc electrode is a new direction developed in recent years and is continuously mature and industrialized; compared with the traditional zinc oxide desulfurizer, the calcium zincate is a normal-temperature desulfurizer with desulfurization active components, and the sulfur capacity is greatly increased; the calcium zincate as the feed additive is not only beneficial to the absorption of animals but also beneficial to reducing the environmental pollution. The calcium zincate can also be widely used for glaze, paint, coating additives and the like. Calcium zincate can also be used as raw material for electrolytic zinc and zinc oxide.
The preparation method of calcium zincate in the prior art is limited to experimental exploration and is not mature. For example, Chinese patents CN1397498A and CN1595688A both disclose the synthesis of calcium zincate by ball milling, among which, Chinese patent CN1397498A discloses that Ca (OH)2And ZnO are put into a ball milling tank according to the proportion in the chemical formula of calcium zincate, a proper amount of water is added,ball-milling for 8-18 hours under the protection of argon atmosphere, and then baking for 10-15 hours at 30-80 ℃ to obtain a product; U.S. Pat. No. 5,460,899 discloses a method of using ZnO and Ca (OH)2A method for generating calcium zincate by reaction in alkali liquor; chinese patent CN2012100305744 discloses a soluble zinc salt and Ca (OH) in a stoichiometric ratio2Preparing into emulsion to generate calcium zincate. In the method, finished high-purity zinc oxide or finished zinc salt is used as a starting raw material, the raw material is expensive, the reaction condition is harsh, the energy consumption is high, the reaction is incomplete, the yield is low, the reaction specificity is poor, the interference of impurities is easy, the total preparation process cost is high, and the method is not suitable for industrial application.
Zinc oxide is an oxide of zinc, is poorly soluble in water, and is soluble in acids and strong bases. Zinc oxide is a commonly used chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint, coating, ointment, adhesive, food, batteries, flame retardant and the like. The zinc oxide has large energy band gap and exciton constraint energy, high transparency and excellent normal temperature luminous performance, and is applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like in the semiconductor field.
Chinese patent CN102863007 discloses a method for producing zinc oxide from leaching residue of electrolytic zincate method, which comprises leaching, purifying, ammonia evaporation crystallization, rinsing, drying and calcining the leaching residue of electrolytic zinc by ammonia-ammonium carbonate to produce zinc oxide, wherein zinc content in the leaching residue of electrolytic zinc is low, zinc concentration in complexing liquid is difficult to exceed 3% in practical application, so that ammonia evaporation energy consumption is too high, and environmental protection processing pressure in the process is increased due to the existence of a large amount of sulfate radicals.
Disclosure of Invention
Problems to be solved by the invention
The technical scheme provided by the disclosure solves the problems that the existing zinc raw material is in shortage, the method for preparing zinc oxide by calcium zincate is good, and the existing method for preparing zinc oxide by leaching residues by an electrolytic zincate method is high in energy consumption, large in environment-friendly treatment pressure and the like.
Means for solving the problems
In order to solve the problems in the prior art, the present disclosure provides a method for producing zinc oxide by leaching residues by an electrolytic zincate method, comprising the following steps:
leaching: mixing and stirring leaching residues obtained by an electrolytic zincate method and a leaching agent, and then filtering to obtain a leaching agent, wherein the leaching agent is a mixed aqueous solution of ammonia and ammonium bicarbonate, or a mixed aqueous solution of ammonia and ammonium carbonate, or a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate;
optionally, purifying the leachate obtained in the leaching step;
and (3) desulfurization: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
calcium zincate synthesis step: adding calcium hydroxide and/or calcium oxide into the first filtrate, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
optionally, rinsing the second solid with water;
and (3) calcining: calcining the second solid at the temperature of 150-1050 ℃, preferably 150-350 ℃;
calcium and zinc separation: and mixing the calcined product obtained in the calcining step with water, stirring, filtering to obtain a third solid and a third filtrate, and drying the third solid to obtain a zinc oxide product.
In the method for producing zinc oxide by using the electrolytic zincate leaching residue, the mass concentration of total ammonia in the leaching agent is 5-15%, and the amount of available carbonate in the leaching agent is 100-200% of the amount of sulfate in the electrolytic zincate leaching residue.
In the method for producing zinc oxide by using the leached residues of the electrolytic zincate method, provided by a further embodiment of the disclosure, the concentration of zinc ammine complex ions (based on the mass of zinc element) in the leached solution obtained in the leaching step is 10-25 g/L.
In the method for producing zinc oxide by using the leaching residue of the electrolytic zincate method, the concentration of zinc ammine complex ions (based on the mass of zinc element) in the leaching solution obtained by filtering is adjusted to 10-25 g/L in the leaching step.
In a method for producing zinc oxide using electrolytic zincate leach residues provided in a further embodiment of the present disclosure, the amount of the substance of calcium oxide and/or calcium hydroxide added in the desulfurization step is 100% to 130%, preferably 100% to 110%, of the amount of the substance of sulfate groups in the leachate.
In the method for producing zinc oxide by using the leached residue of the electrolytic zincate method, in the calcium zincate synthesis step, the ratio of the amount of substances of calcium hydroxide and/or calcium oxide to the amount of substances of zinc ammino ions in the first filtrate is 1-1.2: 2, preferably 1-1.1: 2.
In the method for producing zinc oxide by using the leaching residue of the electrolytic zincate method provided by the further embodiment of the disclosure, carbon dioxide is introduced into the second filtrate obtained in the calcium zincate synthesis step, and the second filtrate introduced with the carbon dioxide is used as a leaching agent and is recycled for leaching the leaching residue of the electrolytic zincate method.
In the method for producing zinc oxide by using the leaching residue of the electrolytic zincate method provided by the further embodiment of the disclosure, the reaction temperature of the calcium zincate synthesis step is 15-90 ℃, preferably 30-60 ℃, or preferably 15-25 ℃.
In the method for producing zinc oxide by using the leaching residue of the electrolytic zincate method provided by the further embodiment of the disclosure, in the calcium-zinc separation step, carbon dioxide is introduced into the third filtrate to obtain calcium carbonate precipitate.
ADVANTAGEOUS EFFECTS OF INVENTION
The present disclosure achieves the following advantageous technical effects in one or more aspects:
1) the sulfate in the leaching slag of the electrolytic zincate method is converted into carbonate, so that the metal salt in the slag is more difficult to dissolve in water, the environmental protection problem is solved, and the secondary utilization of the leaching slag (which can be used as a raw material of cement and fired bricks) is realized.
2) The ammonia such as zinc, copper, cadmium and the like in the leaching residue of the electrolytic zincic acid method can enter the complexing solution by complexing ions, thereby solving the pollution of various heavy metals and realizing the resource utilization of the heavy metals.
3) Calcium oxide or calcium hydroxide is creatively added into an ammonium sulfate-zinc ammonia complex system to move the balance of zinc ammonia complex ions-zinc hydroxide/calcium zincate, thereby realizing the crystallization separation of zinc ions and breaking the inherent method that the traditional ammonia-ammonium bicarbonate method zinc complex leaching process destroys the complex environment by heating and evaporating ammonia to realize the crystallization separation of zinc ions. The process disclosed by the invention is simple and easy to implement without ammonia distillation, and the energy consumption of the process is greatly reduced.
4) Sulfate ions as a pollution source are converted into valuables by calcium sulfate.
5) The synthesis of calcium zincate is realized for the first time in the zinc ammonia environment, and zinc oxide is obtained through the calcium zincate; the reaction selectivity of synthesizing calcium zincate from the zinc ammine complex ions is high, simple and rapid.
6) The process disclosed by the invention realizes leaching and separation of zinc through circulation of carbonate, and solves the environmental protection problem in the existing ammonia circulation process because the surplus water brought by steam influences the process water balance.
7) The method breaks the inherent method that the traditional ammonia-ammonium bicarbonate method zinc complex leaching process destroys the complex environment by heating and evaporating ammonia to realize zinc ion crystallization separation, creatively adds calcium oxide or calcium hydroxide into an ammonium bicarbonate-zinc ammonia complex system to shift the balance of zinc ammonia complex ions-zinc hydroxide/calcium zincate, realizes the selective crystallization separation of zinc element by a balance shift principle on the premise of not destroying the dissolved ammonia environment, and avoids the phenomenon of impurity coprecipitation caused by the ammonia environment destruction of the existing heating and ammonia evaporation method. The process disclosed by the invention is simple and easy to implement without ammonia distillation, greatly reduces the energy consumption of the process, and also avoids the problems of high-temperature and high-pressure potential safety hazards caused by ammonia distillation, equipment corrosion and extra environmental protection treatment burden caused by evaporation and volatilization of a large amount of ammonia.
Detailed Description
Various exemplary embodiments, features and aspects of the disclosure are described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. In some instances, methods, means, reagents and devices well known to those skilled in the art are not described in detail, but those skilled in the art can implement the technical solutions of the present disclosure based on the general knowledge in the art.
Noun interpretation
As used herein, unless otherwise specified, "zinc ammine carbonate" is a generic term for compounds formed from zinc ammine complex ions and carbonate ions, and includes [ Zn (NH)3)4]CO3(Zinc tetraammine carbonate), [ Zn (NH)3)3]CO3(Triammine Zinc carbonate), [ Zn (NH)3)2]CO3(Diaminozinc carbonate), [ Zn (NH)3)]CO3(zinc monoammonium carbonate), and the like.
In this context, unless otherwise stated, "zinc ammine complex ion" is a generic term for each level of ammine zinc complex ion, and includes [ Zn (NH)3)4]2+(Zinc tetraammine ion), [ Zn (NH)3)3]2+(Triammine Zinc ion), [ Zn (NH)3)2]2+(Diaminato zinc ion), [ Zn (NH)3)]2+(zinc ion ammine), and the like.
As used herein, unless otherwise indicated, "carbonate" in a solution (including but not limited to various liquors such as lixiviants, leachate, and the like) refers to the sum of carbonate and bicarbonate in the solution.
"optional" or "optionally" means that the subsequently described step may or may not be performed, and that the expression includes instances where the subsequently described step is performed and instances where the subsequently described step is not performed.
Chemical reaction formula
1. Leaching
a. Replacement of sulfate with carbonate/bicarbonate
CaSO4+(NH4)2CO3＝CaCO3+(NH4)2SO4
MgSO4+(NH4)2CO3＝MgCO3+(NH4)2SO4
PbSO4+(NH4)2CO3＝PbCO3+(NH4)2SO4
Or
CaSO4+NH4HCO3＝CaCO3+(NH4)2SO4+H2O+CO2
MgSO4+NH4HCO3＝MgCO3+(NH4)2SO4+H2O+CO2
PbSO4+NH4HCO3＝PbCO3+(NH4)2SO4+H2O+CO2
b. Zinc oxide leaching
ZnO+(i-2)NH3+(NH4)2SO4＝[Zn(NH3)i]SO4+H2O (i is an integer of 2 to 4) 2 desulfurization
CaO+H2O＝Ca(OH)2
Ca(OH)2++(NH4)2SO4＝CaSO4↓+NH3·H2O
[Zn(NH3)i]SO4+Ca(OH)2＝[Zn(NH3)i](OH)2+CaSO4↓
3. Calcium zincate synthesis
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O＝Ca(OH)2·2Zn(OH)2·2H2O+2iNH3
(i is an integer of 1 to 4)
4. Calcination of
Ca(OH)2·2Zn(OH)2·2H2O＝Ca(OH)2+2ZnO+4H2O
Or
Ca(OH)2·2Zn(OH)2·2H2O＝CaO+2ZnO+5H2O
The concrete process steps
Step 1 extraction
Mixing the leaching residue of electrolytic zincate method with prepared leaching agent according to a certain proportion, stirring and leaching, wherein the leaching agent can be selected from: a mixed aqueous solution of ammonia and ammonium bicarbonate; a mixed aqueous solution of ammonia and ammonium carbonate; a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate. Leaching and filtering to obtain a leaching solution.
The concentration of total ammonia and the concentration of available carbonate in the leaching agent are not particularly limited, and the concentration can be selected by a person skilled in the art according to the factors such as the sulfate content and the zinc content in the leaching residue of the electrolytic zinc acid method of each batch and the actual requirement.
In the preferred scheme, the mass concentration of the total ammonia in the leaching agent is 5-15%, more preferably 6-8%, and the preferred concentration range can achieve sufficient leaching effect and avoid the problems of waste and environmental protection caused by excessive ammonia.
In a preferable scheme, the amount of available carbonate in the leaching agent is approximately matched with the amount of sulfate radicals in the leaching residue of the electrolytic zincic acid method, and a certain excess is allowed so as to achieve the purposes of fully converting sulfate in the leaching residue into carbonate and not excessively increasing the treatment pressure of a subsequent process. For example, the amount of available carbonate in the leaching agent is 100% to 200% of the amount of sulfate in the leaching residue of the electrolytic zinc acid method.
The weight ratio of the leaching agent to the electrolytic zincate process leaching residue is not particularly limited as long as the zinc component can be leached. Preferably, the weight ratio of the leaching agent to the leaching residue of the electrolytic zincate method is 3:1 to 5:1, so that not only can a satisfactory leaching effect be obtained, but also the waste of the leaching agent is avoided.
The leaching temperature is not particularly limited as long as the zinc component in the leaching residue of the electrolytic zincate process is leached. Preferably, the leaching is carried out at ambient temperature, for example at 15 to 30 ℃. The leaching residue of the electrolytic zincate method and the leaching agent are mixed and stirred, the stirring time is not particularly limited, and the stirring time is preferably 1 to 4 hours, more preferably 1 to 2 hours. And filtering after stirring to obtain the leaching solution.
In the leaching process, a plurality of metal sulfates in the leaching residue of the electrolytic zincate method are converted into more insoluble carbonates to be filtered and removed, and zinc elements are converted into zinc ammine complex ions (mainly zinc ammine complex ions at each stage) to enter the leaching solution. The leachate is sent to the subsequent desulfurization process. The concentration of the zinc ammine complex ions in the leachate is not particularly limited, but the concentration (by mass of the zinc element) of the zinc ammine complex ions in the leachate is preferably 10-25 g/L, so that the treatment efficiency of the process can be optimized, good yield and purity can be obtained in the subsequent calcium zincate synthesis step, and the comprehensive economic benefit is optimal. If the concentration of the zinc ammine complex ions in the original leached liquid is not in the preferred range, optionally concentrating or diluting the leached liquid, and adjusting the concentration of the zinc ammine complex ions in the leachate to be in the preferred range of 10-25 g/L.
Step 2 purification
Step 2 is an optional step, and step 2 is optionally performed, if necessary. Purifying the leachate by a known method to remove impurity elements such as iron, manganese, lead, copper and the like. An exemplary purification method is to add zinc powder for displacement and then filtering to remove heavy metal contaminants, but various other known purification methods may be used. The purification step helps to increase the purity of the final product.
Step 3 desulfurization
In the desulfurization step, calcium hydroxide and/or calcium oxide is added into the leachate containing zinc ammine complex ions to convert sulfate radicals in the leachate into insoluble calcium sulfate. If the concentration of the zinc ammine complex ions in the leachate is too high, equilibrium shift of zinc ammine complex ions-zinc hydroxide in the leachate may occur at the same time, and a very small portion of the zinc component may be co-precipitated with calcium sulfate in the form of zinc hydroxide.
In the desulfurization step, calcium hydroxide and/or calcium oxide is added in an amount approximately matching the sulfate radical content in the leachate, for example, the amount of the substance of calcium hydroxide and/or calcium oxide added in the desulfurization step is 100% to 130%, more preferably 100% to 110%, of the amount of the substance of sulfate radical in the leachate. Proper addition of calcium hydroxide and/or calcium oxide is helpful for controlling the process cost and improving the purity and quality of the finished zinc product.
In the desulfurization step, calcium hydroxide and/or calcium oxide is added into the leaching solution, and the mixture is stirred for reaction to generate solid precipitate. The reaction temperature is not particularly limited, but since the reaction can be smoothly carried out without heating, it is particularly preferable to carry out the reaction at room temperature (for example, 15 to 25 ℃), which not only saves energy but also reduces environmental pollution caused by ammonia volatilization. The stirring time is not particularly limited as long as a precipitate is obtained, and stirring is preferably performed for 1 to 2 hours.
And filtering after stirring to obtain a first solid and a first filtrate. The primary component of the first solid is calcium sulphate, and if the concentration of zinc ammine ions in the leach solution is high, some zinc hydroxide co-precipitated with the calcium sulphate may also be present in the first solid. The first filtrate continues to be used for the subsequent calcium zincate synthesis.
Step 4 calcium zincate Synthesis
And adding calcium hydroxide and/or calcium oxide into the first filtrate, and stirring for reaction. The ratio of the amount of the calcium hydroxide and/or calcium oxide to the amount of the zinc ammine complex ion in the first filtrate is preferably 1 to 1.2:2, more preferably 1 to 1.1: 2. The reaction temperature is not particularly limited, and may be, for example, 15 to 90 ℃, preferably 20 to 90 ℃, and more preferably 30 to 60 ℃; or the reaction temperature of 15-25 ℃ is also preferably selected, and the temperature range has the advantages of no need of heating, energy conservation and reduction of ammonia volatilization. Filtering can be carried out after the reaction is carried out for 0.5-2 hours (preferably 0.5-1 hour), and long-time reaction and ageing processes are not needed. Filtering to obtain a second solid and a second filtrate. The main component of the second solid is calcium zincate. In addition, carbon dioxide can be introduced into the second filtrate and then recycled for leaching of the leaching residue of the electrolytic zincate method.
Step 5 calcium zincate rinse
Step 5 is an optional step, and step 5 is optionally performed, if necessary. In the step 5, adding water into the second solid with calcium zincate as a main component for rinsing, wherein the liquid-solid ratio is 5-10: 1, and the rinsing times are 1-2 times.
Step 6 calcination
In this step, the second solid is calcined to decompose the calcium zincate. The calcination temperature is 150-1050 ℃, preferably 150-350 ℃. The product obtained by calcining is a mixture, and if the calcining temperature is 150-350 ℃, the main components of the calcined product are zinc oxide and calcium hydroxide; if higher calcination temperatures are employed, the calcined product may contain zinc oxide, calcium hydroxide, and/or calcium oxide.
Step 7 calcium Zinc separation
Since zinc oxide is difficult to dissolve in water, and calcium hydroxide (or calcium oxide) is soluble in water or soluble in water after reaction with water, the separation of zinc oxide and calcium hydroxide (or calcium oxide) can be realized by utilizing the water solubility difference of zinc oxide and calcium hydroxide (or calcium oxide).
In this step, the calcined product obtained in step 6 is mixed with water, stirred, and filtered to obtain a third solid and a third filtrate. The solute in the third filtrate is mainly calcium hydroxide, carbon dioxide can be introduced into the third filtrate to obtain calcium carbonate precipitate, and the third filtrate can also be recycled for other purposes. And drying the third solid to obtain a zinc oxide product.
Embodiments of the present disclosure will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The zinc content of the leaching residue of the electrolytic zinc acid method of Sichuan company is 8.46 percent, and the sulfur content is 14.09 percent.
200 g of electrolytic zinc acid leaching residue is put into 1000 ml of ammonia-ammonium carbonate mixed solution (the total ammonia mass concentration is 10%, and the carbonate mass concentration is 5.5%) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc content (calculated by zinc oxide equivalent) in the filtered liquid is 1.47%, and the sulfate radical mass concentration in the liquid is 8.8%. According to the inspection data, the zinc recovery rate is 86.9%.
And purifying the filtered zinc-ammonia complex solution.
500 ml of purified zinc-ammonia complex solution is taken, 25.67 g of calcium oxide is added for precipitating sulfate radicals, and filtration is carried out after reaction for 1 hour.
1.8 g of calcium hydroxide was added to the filtered liquid for calcium zincate synthesis, and the mixture was stirred for 1 hour and then filtered. The solid obtained by filtering is dried for 2 hours at 105 ℃, and then calcined for 2 hours at 300 ℃, and the calcium zincate is decomposed into zinc oxide and calcium hydroxide.
Adding 300 times of water by mass into zinc oxide and calcium hydroxide, stirring for 1 hour, filtering, drying the filtered zinc oxide at 105 ℃ for 2 hours, and detecting and analyzing to obtain the product with the zinc oxide content of 99.56%.
Example 2
The zinc content of the leaching residue obtained by the electrolytic zinc acid method of a company in Yunnan is 7.98 percent, and the sulfur content is 16.01 percent.
200 g of electrolytic zinc acid leaching residue is put into 1000 ml of ammonia-ammonium carbonate mixed solution (the total ammonia mass concentration is 10 percent, and the carbonate mass concentration is 6 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc content (calculated by zinc oxide equivalent) in the filtered liquid is 1.367 percent, and the sulfate radical mass concentration in the liquid is 9.61 percent. According to the inspection data, the zinc recovery rate is 86.63%.
And purifying the filtered zinc-ammonia complex solution.
And taking 500 ml of purified zinc-ammonia complex solution, adding 28 g of calcium oxide for precipitating sulfate radicals, reacting for 1 hour, and filtering.
1.6 g of calcium hydroxide was added to the filtered liquid for calcium zincate synthesis, and the mixture was stirred for 1 hour and then filtered. The solid obtained by filtering is dried for 2 hours at 105 ℃, and then calcined for 2 hours at 300 ℃, and the calcium zincate is decomposed into zinc oxide and calcium hydroxide.
Adding water 300 times the mass of zinc oxide and calcium hydroxide, stirring for 1 hour, filtering, drying the filtered zinc oxide at 105 ℃ for 2 hours, and detecting and analyzing to obtain the product with the zinc oxide content of 99.47%.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (14)
1. The method for producing zinc oxide by using the leaching residues of the electrolytic zincic acid method is characterized by comprising the following steps of:
leaching: mixing and stirring leaching residues obtained by an electrolytic zincate method and a leaching agent, and then filtering to obtain a leaching agent, wherein the leaching agent is a mixed aqueous solution of ammonia and ammonium bicarbonate, or a mixed aqueous solution of ammonia and ammonium carbonate, or a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate;
optionally, purifying the leachate obtained in the leaching step;
and (3) desulfurization: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
calcium zincate synthesis step: adding calcium hydroxide and/or calcium oxide into the first filtrate, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
optionally, rinsing the second solid with water;
and (3) calcining: calcining the second solid at the temperature of 150-1050 ℃;
calcium and zinc separation: and mixing the calcined product obtained in the calcining step with water, stirring, filtering to obtain a third solid and a third filtrate, and drying the third solid to obtain a zinc oxide product.
2. The method for producing the zinc oxide by using the leaching residue of the electrolytic zincate acid method according to claim 1, wherein in the calcining step, the calcining temperature is 150-350 ℃.
3. The method for producing zinc oxide by using the leached residues of the electrolytic zinc acid method according to claim 1, characterized in that the mass concentration of total ammonia in the leaching agent is 5-15%, and the amount of available carbonate in the leaching agent is 100-200% of the amount of sulfate in the leached residues of the electrolytic zinc acid method.
4. The method for producing zinc oxide by using the leached residues of the electrolytic zincate process according to any one of claims 1 to 3, wherein the concentration of the zinc ammine complex ions in terms of the mass of zinc element in the leached solution obtained in the leaching step is 10 to 25 g/L.
5. The method for producing zinc oxide by using the leached residues of the electrolytic zincate process according to any one of claims 1 to 3, characterized in that in the leaching step, the concentration of zinc ammine ions in the leached solution obtained by filtration is adjusted to 10 to 25g/L in terms of the mass of zinc element.
6. The method for producing zinc oxide by using the electrolytic zincate leach residue according to any one of claims 1 to 3, wherein the amount of the substance of calcium oxide and/or calcium hydroxide added in the desulfurization step is 100 to 130% of the amount of the substance of sulfate radical in the leachate.
7. The method for producing zinc oxide by using the leached residues of the electrolytic zincate process according to claim 6, characterized in that the amount of the substance of calcium oxide and/or calcium hydroxide added in the desulfurization step is 100 to 110% of the amount of the substance of sulfate radical in the leached solution.
8. The method for producing zinc oxide by using the leached residues of the electrolytic zincate process according to any one of claims 1 to 3, wherein in the calcium zincate synthesis step, the ratio of the amount of the substance of calcium hydroxide and/or calcium oxide added to the first filtrate to the amount of the substance of zinc ammine complex ion in the first filtrate is 1-1.2: 2.
9. The method for producing zinc oxide by using the leached residue of the electrolytic zincate process according to claim 8, wherein in the calcium zincate synthesizing step, the ratio of the amount of the substance of calcium hydroxide and/or calcium oxide to the amount of the substance of zinc ammine complex ion in the first filtrate is 1-1.1: 2.
10. The method for producing zinc oxide by using electrolytic zincate leaching residues according to any one of claims 1 to 3, wherein carbon dioxide is introduced into the second filtrate obtained in the calcium zincate synthesizing step, and the second filtrate introduced with carbon dioxide is used as a leaching agent to be recycled for leaching of the electrolytic zincate leaching residues.
11. The method for producing zinc oxide by using the leaching residue of the electrolytic zincate method according to any one of claims 1 to 3, wherein the reaction temperature of the calcium zincate synthesis step is 15-90 ℃.
12. The method for producing zinc oxide by using the leaching residue of the electrolytic zincate method according to claim 11, wherein the reaction temperature of the calcium zincate synthesis step is 30-60 ℃.
13. The method for producing zinc oxide by using the leaching residue of the electrolytic zincate method according to claim 11, wherein the reaction temperature of the calcium zincate synthesis step is 15-25 ℃.
14. The method for producing zinc oxide by using the leached residues of the electrolytic zincate process according to any one of claims 1 to 3, wherein in the calcium-zinc separation step, carbon dioxide is introduced into the third filtrate to obtain calcium carbonate precipitate.
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Effective date of registration: 20201123 Address after: Chongqing Dongqun Technology Co., Ltd., No. 33, Jiangxi Road, Nan'an District, Chongqing Patentee after: CHONGQING DONGQUN TECHNOLOGY Co.,Ltd. Address before: 100142 1603, 17 floor, Ding Hui East Lane, Haidian District, Beijing. Patentee before: Sun Xiaoming |