CN115386734B - Method for producing zinc ingot by high-chlorine zinc ash - Google Patents
Method for producing zinc ingot by high-chlorine zinc ash Download PDFInfo
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- CN115386734B CN115386734B CN202211010330.XA CN202211010330A CN115386734B CN 115386734 B CN115386734 B CN 115386734B CN 202211010330 A CN202211010330 A CN 202211010330A CN 115386734 B CN115386734 B CN 115386734B
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000011701 zinc Substances 0.000 title claims abstract description 94
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 94
- 239000000460 chlorine Substances 0.000 title claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002893 slag Substances 0.000 claims abstract description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims description 93
- 239000002253 acid Substances 0.000 claims description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 48
- 238000001914 filtration Methods 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052785 arsenic Inorganic materials 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- 238000006298 dechlorination reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- ICGLOTCMOYCOTB-UHFFFAOYSA-N [Cl].[Zn] Chemical compound [Cl].[Zn] ICGLOTCMOYCOTB-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- 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)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for producing zinc ingots by high-chlorine zinc ash, which can recover zinc and chlorine, is used for production, has a short flow, can realize the purpose of comprehensive utilization of resources, and simultaneously recovers the chlorine to produce ammonium chloride which is used as a slag former in zinc sheet smelting so as to realize comprehensive utilization of wastes.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for producing zinc ingots by using high-chlorine zinc ash.
Background
At present, the domestic zinc ash recovery method mostly adopts a pyrogenic method, and the technical report of producing zinc ingots by adopting a wet process is less.
The patent of application number 201110121965.2, "method for recovering zinc by zinc ash smelting", and smelting device for implementing the method ", (1) putting zinc ash into a zinc pot, and covering the pot cover; heating the zinc pot to 485+/-5 ℃ within 4-8 hours, stopping heating, and preserving the heat for 3 hours; stirring zinc ash in the pot by using a stirrer; preserving heat for 1 hour, and stirring once; and then preserving the heat for 1 hour, and then fishing out the zinc sinking into the bottom of the pot. The method utilizes a special smelting device to precipitate zinc liquid in zinc ash through heating smelting, heat preservation and stirring of the zinc ash. By implementing the method, more than 90% of zinc in zinc ash can be conveniently collected while the zinc is produced in the zinc plating production, and the purity of refined zinc is more than 98% by detection. The zinc ingot produced by the process contains more than 98% of zinc, has higher chlorine content, and can be processed to produce 99.995% zinc ingot.
The patent of application number 201010567399.3, "a process for recovering zinc from hot-dip zinc ash", wherein the hot-dip zinc ash is subjected to dry grinding and screening, and then separated to obtain a metal zinc-containing oversize product and a zinc oxide-containing undersize product, so that the metal zinc and the zinc oxide of the hot-dip zinc ash are subjected to preliminary separation; the oversize material is treated with unbound water and zinc chloride at 400-500 deg.c and vacuum degree of 10-50 Pa, and then vacuum distilled at 650-800 deg.c and vacuum degree of 10-30 Pa to obtain zinc metal; after the undersize is subjected to alkali washing and dechlorination, using ferrosilicon as a reducing agent and calcium oxide as a slag former, and carrying out vacuum thermal reduction on zinc oxide to obtain metallic zinc under the conditions that the vacuum degree is 10-30 Pa and the temperature is 1050-1200 ℃. The process flow is long and the energy consumption is high.
Disclosure of Invention
In order to solve or partially solve the problems existing in the related art, the invention provides a method for producing zinc ingots by using high-chlorine zinc ash. Meanwhile, the recycling of chlorine to produce ammonium chloride, which is used as a slag former in zinc sheet smelting, is a main purpose of the process.
The invention provides a method for producing zinc ingots by high-chlorine zinc ash, which comprises the following steps:
s1, oxidation: slurrying zinc ash and water, adding hydrogen peroxide for oxidization, and standing for oxidization for 0.5-1.5 h;
s2 dechlorination: the liquid-solid ratio is raised to 2-6: 1 adding ammonia water for dechlorination, filtering, and then filtering residues according to a liquid-solid ratio of 2-6: 1 pulp mixing and sulfuric acid leaching, wherein the leaching temperature is 60-90 ℃, the leaching time is 2-4 h, and the terminal pH value is as follows: 2.0 to 5.0, and then filtering to produce low-acid leaching solution and first-stage acid leaching slag;
s3, treating acid leaching residues at one stage, adding hydrogen peroxide into the acid leaching residues for oxidation, and then, according to a liquid-solid ratio of 2-6: 1 adding sulfuric acid for leaching, wherein the acid leaching is controlled at 70-100 ℃ for 1-3 h, and the terminal pH value is as follows: 1.0 to 2.0, filtering after leaching, returning the leaching solution of the second stage to the zinc ash leaching stage for liquid supplementing, and selling acid leaching residues;
s4, primary purification of low-acid leaching liquor: adding hydrogen peroxide 0.01-0.03L/L, fully oxidizing, heating the solution to 50-70 ℃, adding lime, regulating the pH of the end point to 4.0-6.0, hydrolyzing and precipitating Fe and As, heating the solution to 70-90 ℃ without filtering, adding KMnO 4 Oxidizing manganese ions to form manganese dioxide precipitates;
s5, secondary purification of low-acid leaching liquor: adding zinc powder to remove heavy metal ions Cd and Cu in the solution by replacement, wherein the replacement control conditions are as follows: the temperature is 50-70 ℃ and the reaction time is 0.5-1.5 h;
s6, electrodeposition: electro-deposition is carried out on the purified zinc sulfate solution to produce zinc sheets;
s7, casting: the zinc sheet is melted, and after adding ammonium chloride to carry out slag formation, ingots are cast into 99.995 percent zinc ingots.
Further, in the step S1, the zinc ash contains 60 to 80 percent of zinc, 1 to 2 percent of chlorine, 0.005 to 0.015 percent of fluorine and 0.001 to 0.02 percent of arsenic.
Further, in the step S1, the zinc ash and water are mixed according to a liquid-solid ratio of 1-3: 1.
further, the hydrogen peroxide in the step S1 is added in an amount of 0.1-0.3 mL/g.
Further, the zinc powder in the step S5 is added in an amount which is 1.05 to 1.2 times the mass of the heavy metal salt.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.
The beneficial technical effects of the invention are as follows:
1. the invention adopts oxidative dechlorination to produce ammonium chloride, which is used for zinc sheet melting and slagging, thus achieving comprehensive utilization of waste.
2. The invention can directly return zinc ash to the main flow for producing zinc sulfate solution to produce 99.995% zinc ingot, and has simple process flow, easy control, lower cost and novel thought.
Drawings
FIG. 1 is a flow chart of an implementation of one embodiment of the present application;
Detailed Description
Alternative embodiments of the present application will be described in more detail below with reference to the accompanying drawings. While the drawings illustrate alternative embodiments of the present application, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
The liquid-solid ratio in the application of the invention refers to the ratio of the mass of a solution to the mass of a solid material in a reaction system.
The method for producing zinc ingots by using the high-chlorine zinc ash disclosed by the invention is described in detail below with reference to the accompanying drawings, and is specifically as follows:
the method for producing zinc ingots by using the high-chlorine zinc ash comprises the following steps:
s1, oxidation: slurrying zinc ash and water, adding hydrogen peroxide for oxidization, and standing for oxidization for 0.5-1.5 h;
s2 dechlorination: the liquid-solid ratio is raised to 2-6: 1 adding ammonia water for dechlorination, filtering, and then filtering residues according to a liquid-solid ratio of 2-6: 1 pulp mixing and sulfuric acid leaching, wherein the leaching temperature is 60-90 ℃, the leaching time is 2-4 h, and the terminal pH value is as follows: 2.0 to 5.0, and then filtering to produce low-acid leaching solution and first-stage acid leaching slag;
s3, treating acid leaching residues at one stage, adding hydrogen peroxide into the acid leaching residues for oxidation, and then, according to a liquid-solid ratio of 2-6: 1 adding sulfuric acid for leaching, wherein the acid leaching is controlled at 70-100 ℃ for 1-3 h, and the terminal pH value is as follows: 1.0 to 2.0, filtering after leaching, returning the leaching solution of the second stage to the zinc ash leaching stage for liquid supplementing, and selling acid leaching residues;
s4, primary purification of low-acid leaching liquor: adding hydrogen peroxide 0.01-0.03L/L, fully oxidizing, heating the solution to 50-70 ℃, adding lime, regulating the pH of the end point to 4.0-6.0, hydrolyzing and precipitating Fe and As, heating the solution to 70-90 ℃ without filtering, adding KMnO 4 Oxidizing manganese ions to form manganese dioxide precipitates; adding KMnO 4 As a strong oxidant, manganese ions can be oxidized to form manganese dioxide precipitates; the ferrous iron can be converted into trivalent iron, the trivalent iron is easy to hydrolyze, and the ferric iron is completely hydrolyzed into ferric hydroxide precipitate when the pH value is more than 4, and the oxidation end point is reached when the color of the solution becomes reddish.
S5, secondary purification of low-acid leaching liquor: adding zinc powder to remove heavy metal ions Cd and Cu in the solution by replacement, wherein the replacement control conditions are as follows: the temperature is 50-70 ℃ and the reaction time is 0.5-1.5 h;
s6, electrodeposition: electro-deposition is carried out on the purified zinc sulfate solution to produce zinc sheets;
s7, casting: the zinc sheet is melted, and after adding ammonium chloride to carry out slag formation, ingots are cast into 99.995 percent zinc ingots.
In one embodiment of the present application, the zinc ash in step S1 contains zinc 60-80%, chlorine 1-2%, fluorine 0.005-0.015%, and arsenic 0.001-0.02%.
In one embodiment of the present application, the zinc ash and water in step S1 are mixed according to a liquid-solid ratio of 1 to 3:1.
in one embodiment of the present application, the hydrogen peroxide in the step S1 is added in an amount of 0.1-0.3 mL/g.
In one embodiment of the present application, the zinc powder is added in the step S5 in an amount of 1.05 to 1.2 times by mass of the heavy metal salt.
For clarity, the following examples are provided in detail.
Example 1
The high-chlorine zinc ash containing 60 percent of zinc, 2 percent of chlorine, 0.015 percent of fluorine and 0.02 percent of arsenic and water are mixed according to a liquid-solid ratio of 3:1 (mass ratio), adding hydrogen peroxide for oxidation, wherein the adding amount of the hydrogen peroxide is 0.3mL/g, and standing for oxidation for 1.5h. The liquid-solid ratio is raised to 6: adding ammonia water for dechlorination, filtering, and filtering residues according to a liquid-solid ratio of 6:1 (mass ratio) mixing pulp, adding sulfuric acid for leaching, wherein the leaching temperature is 90 ℃, the leaching time is 4 hours, and the end point pH is 5. Filtering to obtain low-acid leaching solution and first-stage acid leaching slag. Treating acid leaching slag in one stage, adding hydrogen peroxide into the acid leaching slag for oxidation, and then, according to a liquid-solid ratio of 6:1 (mass ratio) adding sulfuric acid for leaching, controlling the acid leaching temperature to be 100 ℃, controlling the acid leaching time to be 3h, controlling the end point pH to be 2.0, filtering after leaching, returning the two-stage leaching liquid to a zinc ash leaching stage for liquid supplementing, and carrying out acid leaching slag export.
Adding hydrogen peroxide 0.03L/L into the low-acid leaching solution for primary purification, fully oxidizing, heating the solution to 70 ℃, adding lime, adjusting the pH of the end point to 6.0, hydrolyzing and precipitating Fe and As, heating the solution to 90 ℃ without filtering, adding KMnO 4 Oxidizing manganese ions to form manganese dioxide precipitate, changing the color of the solution into purplish, and reaching the oxidation end point.
After primary purification, zinc powder is added into the low-acid leaching solution to carry out displacement to remove heavy metal ions Cd and Cu in the solution, the addition amount of the zinc powder is 1.2 times of that of impurities, and the displacement control conditions are as follows: the temperature is 70 ℃ and the reaction time is 1.5h.
And (3) carrying out electrodeposition on the purified zinc sulfate solution to produce zinc sheets. The zinc sheet is melted, and after adding ammonium chloride to carry out slag formation, ingots are cast into 99.995 percent zinc ingots.
Example 2
Zinc-containing 70%, chlorine 1.5%, fluorine 0.0075%, arsenic 0.01% high chlorine zinc ash and water according to a liquid-solid ratio of 2:1 (mass ratio), adding hydrogen peroxide for oxidization, wherein the adding amount of the hydrogen peroxide is 0.2mL/g, and standing for oxidization for 1h. The liquid-solid ratio is raised to 4: adding ammonia water for dechlorination, filtering, and filtering residues according to a liquid-solid ratio of 4:1 (mass ratio) mixing pulp, adding sulfuric acid for leaching, wherein the leaching temperature is 75 ℃, the leaching time is 3h, and the end point pH is 3.5. Filtering to obtain low-acid leaching solution and first-stage acid leaching slag. Treating acid leaching slag in one stage, adding hydrogen peroxide into the acid leaching slag for oxidation, and then, according to a liquid-solid ratio of 4:1 (mass ratio) adding sulfuric acid for leaching, controlling the acid leaching temperature to be 85 ℃, controlling the acid leaching time to be 2h, controlling the end point pH to be 1.5, filtering after leaching, returning the second-stage leaching liquid to the zinc ash leaching stage for liquid supplementing, and carrying out acid leaching slag export.
Adding hydrogen peroxide 0.02L/L into the low-acid leaching solution for primary purification, heating the solution to 60 ℃ after full oxidation, adding lime, adjusting the pH of the end point to 5.0, hydrolyzing and precipitating Fe and As, heating the solution to 80 ℃ without filtering, adding KMnO 4 Oxidizing manganese ions to form manganese dioxide precipitate, changing the color of the solution into purplish, and reaching the oxidation end point.
After primary purification, zinc powder is added into the low-acid leaching solution to carry out displacement to remove heavy metal ions Cd and Cu in the solution, the addition amount of the zinc powder is 1.13 times of that of impurities, and the displacement control conditions are as follows: the temperature is 60 ℃ and the reaction time is 1.0h.
And (3) carrying out electrodeposition on the purified zinc sulfate solution to produce zinc sheets. The zinc sheet is melted, and after adding ammonium chloride to carry out slag formation, ingots are cast into 99.995 percent zinc ingots.
Example 3
Zinc-containing 80%, chlorine 1.0%, fluorine 0.005%, arsenic 0.001% high chlorine zinc ash and water are mixed according to a liquid-solid ratio of 1:1 (mass ratio), adding hydrogen peroxide for oxidation, wherein the adding amount of the hydrogen peroxide is 0.1mL/g, and standing for oxidation for 0.5h. The liquid-solid ratio is raised to 2: adding ammonia water for dechlorination, filtering, and filtering residues according to a liquid-solid ratio of 2:1 (mass ratio) mixing pulp, adding sulfuric acid for leaching, wherein the leaching temperature is 60 ℃, the leaching time is 2h, and the end point pH is 2.0. Filtering to obtain low-acid leaching solution and first-stage acid leaching slag. Treating acid leaching slag in one stage, adding hydrogen peroxide into the acid leaching slag for oxidation, and then, according to a liquid-solid ratio of 2:1 (mass ratio) adding sulfuric acid for leaching, controlling the acid leaching temperature to 70 ℃, controlling the acid leaching time to 1h, controlling the end point pH to 1.0, filtering after leaching, returning the second-stage leaching liquid to the zinc ash leaching stage for liquid supplementing, and carrying out acid leaching slag export.
Adding hydrogen peroxide 0.01L/L into the low-acid leaching solution for primary purification, heating the solution to 50 ℃ after full oxidation, adding lime, adjusting the pH of the end point to 4.0, hydrolyzing and precipitating Fe and As, heating the solution to 70 ℃ without filtering, adding KMnO 4 Oxidizing manganese ions to form manganese dioxide precipitate, changing the color of the solution into purplish, and reaching the oxidation end point.
After primary purification, zinc powder is added into the low-acid leaching solution to be displaced to remove heavy metal ions Cd and Cu in the solution, the addition amount of the zinc powder is 1.05 times of that of impurities, and the displacement control conditions are as follows: the temperature is 50 ℃ and the reaction time is 0.5h.
And (3) carrying out electrodeposition on the purified zinc sulfate solution to produce zinc sheets. The zinc sheet is melted, and after adding ammonium chloride to carry out slag formation, ingots are cast into 99.995 percent zinc ingots.
The foregoing description of the embodiments of the present application is illustrative, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the improvement of technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (5)
1. The method for producing the zinc ingot by using the high-chlorine zinc ash is characterized by comprising the following steps of:
s1, oxidation: slurrying zinc ash and water, adding hydrogen peroxide for oxidization, and standing for oxidization for 0.5-1.5 h;
s2 dechlorination: the liquid-solid ratio is raised to 2-6: 1 adding ammonia water for dechlorination, filtering, and then filtering residues according to a liquid-solid ratio of 2-6: 1 pulp mixing and sulfuric acid leaching, wherein the leaching temperature is 60-90 ℃, the leaching time is 2-4 h, and the terminal pH value is as follows: 2.0 to 5.0, and then filtering to produce low-acid leaching solution and first-stage acid leaching slag;
s3, treating acid leaching residues at one stage, adding hydrogen peroxide into the acid leaching residues for oxidation, and then, according to a liquid-solid ratio of 2-6: 1 adding sulfuric acid for leaching, wherein the acid leaching is controlled at 70-100 ℃ for 1-3 h, and the terminal pH value is as follows: 1.0 to 2.0, filtering after leaching, returning the leaching solution of the second stage to the zinc ash leaching stage for liquid supplementing, and selling acid leaching residues;
s4, primary purification of low-acid leaching liquor: adding hydrogen peroxide 0.01-0.03L/L, fully oxidizing, heating the solution to 50-70 ℃, adding lime, regulating the pH of the end point to 4.0-6.0, hydrolyzing and precipitating Fe and As, heating the solution to 70-90 ℃ without filtering, adding KMnO 4 Oxidizing manganese ions to form manganese dioxide precipitates;
s5, secondary purification of low-acid leaching liquor: adding zinc powder to remove heavy metal ions Cd and Cu in the solution by replacement, wherein the replacement control conditions are as follows: the temperature is 50-70 ℃ and the reaction time is 0.5-1.5 h;
s6, electrodeposition: electro-deposition is carried out on the purified zinc sulfate solution to produce zinc sheets;
s7, casting: the zinc sheet is melted, and after adding ammonium chloride to carry out slag formation, ingots are cast into 99.995 percent zinc ingots.
2. The method for producing zinc ingots by using the high-chlorine zinc ash according to claim 1, wherein the zinc ash in the step S1 contains 60 to 80 percent of zinc, 1 to 2 percent of chlorine, 0.005 to 0.015 percent of fluorine and 0.001 to 0.02 percent of arsenic.
3. The method for producing zinc ingots by using high-chlorine zinc ash according to claim 1, wherein the zinc ash and water in the step S1 are mixed according to a liquid-solid ratio of 1-3: 1.
4. the method for producing zinc ingots by using high-chlorine zinc ash according to claim 1, wherein the hydrogen peroxide in the step S1 is added in an amount of 0.1-0.3 mL/g.
5. The method for producing zinc ingots by using high-chlorine zinc ash according to claim 1, wherein the zinc powder is added in the step S5 in an amount which is 1.05 to 1.2 times the mass of the heavy metal salt.
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| US4355009A (en) * | 1980-05-29 | 1982-10-19 | Southwire Company | Separative treatment of zinc-bearing flue dust |
| EP0935005A1 (en) * | 1998-02-05 | 1999-08-11 | Bisol S.p.A. | Process for treating metallic dust, mostly oxididised waste, in particular galvanising dust and/or steelworks smoke |
| CN106381397A (en) * | 2016-09-27 | 2017-02-08 | 吉首市金湘资源科技开发有限公司 | Method for dechlorinating through zinc ash material ammonia-leaching ion exchange combined process |
| CN107555469A (en) * | 2017-08-26 | 2018-01-09 | 麻江县金泰工业废渣综合利用回收有限责任公司 | A kind of technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia |
| CN108823420A (en) * | 2018-07-06 | 2018-11-16 | 陕西瑞凯环保科技有限公司 | The method of chlorine is removed in a kind of metallurgical slag |
| CN112522520A (en) * | 2020-12-02 | 2021-03-19 | 陕西锌业有限公司 | Method for directly producing electrolytic zinc by using secondary zinc oxide |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4355009A (en) * | 1980-05-29 | 1982-10-19 | Southwire Company | Separative treatment of zinc-bearing flue dust |
| EP0935005A1 (en) * | 1998-02-05 | 1999-08-11 | Bisol S.p.A. | Process for treating metallic dust, mostly oxididised waste, in particular galvanising dust and/or steelworks smoke |
| CN106381397A (en) * | 2016-09-27 | 2017-02-08 | 吉首市金湘资源科技开发有限公司 | Method for dechlorinating through zinc ash material ammonia-leaching ion exchange combined process |
| CN107555469A (en) * | 2017-08-26 | 2018-01-09 | 麻江县金泰工业废渣综合利用回收有限责任公司 | A kind of technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia |
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| CN112522520A (en) * | 2020-12-02 | 2021-03-19 | 陕西锌业有限公司 | Method for directly producing electrolytic zinc by using secondary zinc oxide |
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