CN115028190A - Preparation method of active zinc oxide - Google Patents
Preparation method of active zinc oxide Download PDFInfo
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- CN115028190A CN115028190A CN202210677604.4A CN202210677604A CN115028190A CN 115028190 A CN115028190 A CN 115028190A CN 202210677604 A CN202210677604 A CN 202210677604A CN 115028190 A CN115028190 A CN 115028190A
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- ammonia
- zinc oxide
- zinc
- leaching
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000002386 leaching Methods 0.000 claims abstract description 55
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000000746 purification Methods 0.000 claims abstract description 23
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 37
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- NSEQHAPSDIEVCD-UHFFFAOYSA-N N.[Zn+2] Chemical compound N.[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000008237 rinsing water Substances 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 4
- 235000020679 tap water Nutrition 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 32
- 239000002351 wastewater Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940105847 calamine Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000001039 zinc pigment Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- C01P2006/12—Surface area
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a preparation method of active zinc oxide, which belongs to the technical field of zinc oxide materials and comprises the steps of ammonia-ammonium liquid leaching, impurity removal and purification, precipitation, pyrolysis ammonia distillation, drying and calcination and the like. The preparation method of the active zinc oxide disclosed by the invention has the advantages of short process flow, strong equipment universality, low investment, capability of recycling the leaching solution ammonia water, low cost and no pollution to the environment. The method has the advantages of simple equipment, low cost, simple impurity removal process, short flow, recyclable ammonia water, strong raw material adaptability and the like.
Description
Technical Field
The invention belongs to the technical field of zinc oxide materials, and particularly relates to a preparation method of active zinc oxide.
Background
The active zinc oxide is mainly used as reinforcing agent and activator in rubber and cable industry, colorant and filler of white glue, as vulcanizing agent in chloroprene rubber, and also can be used in paint, enamel and other zinc pigments, and also can be used in industries of electronics, ceramics, catalyst, etc. The coating is mainly applied to the functions of tinting strength, hiding power, corrosion resistance, luminescence and the like in the coating industry, is used as a dye-proofing agent in the printing and dyeing industry, and is used as a feed additive in the feed industry. In addition, activated zinc oxide is used as a raw material for the production of opal glasses, zinc white-type oil and water color pigments, as well as cosmetics and various zinc salts. Activated zinc oxide first appeared in 1925 and the first production method was to spray a zinc nitrate solution onto a zeolite heated by a hot gas stream to produce activated zinc oxide. The industrial preparation method of the active zinc oxide mainly comprises a sulfuric acid method, a hydrochloric acid method and the like. The industrial production method of zinc oxide includes a dry method and a wet method. The dry process includes both direct and indirect processes. The direct method is to take calamine, zinc sulfide ore, sphalerite, zinc hypoxide ore and the like as raw materials, add a reducing agent, directly calcine the produced zinc steam at high temperature to contact with hot air for oxidation to produce zinc oxide, the product quality is relatively unstable, the indirect method is to refine the zinc ore into zinc ingots firstly, then produce the zinc oxide by the zinc ingots, the cost of the method is too high, and the development is limited. Chinese patent CN201810357132.8 discloses a method for preparing feed-grade active zinc oxide, concentrated sulfuric acid is used as a leaching agent, the usage amount of sulfuric acid is large, thus the difficulty of treatment and environmental protection of subsequent processes is large, leaching with sulfuric acid is used, all equipment must be acid-resistant and corrosion-resistant, when zinc oxide is leached with broken acid, the reaction is performed at a pH value below 5.4, so that the equipment is seriously corroded, acid mist also brings a harsh operating environment to people, harm is brought to human health and surrounding crops, sulfate ions need to be removed, washing is required for many times, water consumption is large, and cost is high. Therefore, those skilled in the art are in urgent need to develop a method for preparing active zinc oxide to overcome the defects of the prior art, so as to meet the existing market demand and performance requirement.
Disclosure of Invention
In view of the defects of the prior art, the invention mainly aims to provide a preparation method of active zinc oxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing active zinc oxide comprises leaching zinc suboxide with ammonia-ammonium solution to obtain zinc oxide leachate, removing impurities, and purifying to obtain ammonia leachate; adding a precipitator into the ammonia leaching purification solution, stirring and reacting at normal temperature for 30-50 min, standing for 10-20 min, performing liquid-solid separation to obtain zinc ammonium double salt intermediate slurry, performing pyrolysis ammonia distillation and slurry rinsing and filter pressing, rinsing the slurry in a rinsing tank, wherein rinsing water is fresh tap water for 1-2 times, performing solid-liquid separation, drying a filter cake after filter pressing by using a flash evaporation dryer, dehydrating and drying wet materials to obtain the zinc ammonium double salt intermediate slurry, and calcining the dried material in a calcining furnace at 550 ℃ for 2.5-3 h to obtain the high-purity zinc oxide.
Further, in the zinc hypoxide ammonia-ammonium liquid [ CO ] 2 ]And [ NH ] 3 ]The molar concentration ratio of the zinc oxide is 1: 3-4, the zinc oxide is prepared by adding water into concentrated ammonia water, ammonium carbonate or ammonium bicarbonate, the total ammonia concentration is 3-6 mol/L to the zinc oxide, and the leaching temperature is 40 ℃; the liquid-solid ratio L: S =3:1, and the leaching time is 1-2 h.
Zinc ammonia complex Zn (NH) generated by reaction 3 ) 4 CO 3 H 2 O can stably exist in liquid phase, the leaching slurry is subjected to liquid-solid separation through a filter press, so that zinc is separated into the filtered liquid phase, and the rest components (Fe, Pb, Mg and SiO) are 2 S, C, etc.) are left in the residue. The filter residue contains part of water-soluble zinc, the part of filter residue is collected into a residue washing pool, then the part of filter residue is rinsed for 2-3 times by using generated rinsing wastewater and then is subjected to filter pressing, the obtained rinsing water returns to the ammonia-ammonium liquid leaching step after passing through an ammonia absorption tower, and the leaching liquid phase rich in the zinc-ammonia complex is purified and purified continuously.
And (4) conveying the leached solution to a purification tank for impurity removal and purification treatment. The impurity removal and purification are two zinc powder replacement and precipitation processes. Firstly, the difference of the potential of the standard electrode of heavy metal ions in leaching solution is utilized, and active zinc powder is added to replace lead, copper, cadmium and the like in the leaching solution. The chemical reaction formula is as follows:
Me(NH 3 ) 4 2+ +Zn=Zn(NH 3 ) 4 2+ +Me↓
adding harmful elements such As Fe, Mn, As and the like in the press filtrate by adding KMnO 4 Making As in the replacement liquid mainly be FeAsO 4 3- Form precipitation; meanwhile, Fe (OH) 3 Colloid with positive charge, AsO 4 3- Can also be substituted by Fe (OH) 3 The colloidal nucleus is adsorbed and then settled together, so that most of arsenic in the leaching solution is removed. The chemical reaction formula is as follows:
5Fe 2+ +MnO4 - +11H 2 O=Mn 2+ +7H + +5Fe(OH) 3 ↓
3Mn 2+ +2MnO4 - +7H 2 O=4H + +5MnO(OH) 2 ↓
Fe 3+ +AsO 4 3- = FeAsO 4 ↓
the oxidation impurity removal liquid contains low-content heavy metal elements, and excessive zinc powder is adopted for secondary replacement to ensure that the mother liquid is qualified. The purified liquid is filtered by pressure (sealed chamber filter press), and the filtrate is firstly sent into a storage tank for storage and then enters the ammonia distillation process.
Collecting the purification and impurity removal slag generated in the purification and impurity removal process into a slag washing tank, rinsing for 1-2 times by using rinsing wastewater in the post-project procedure, and then performing filter pressing;
the purified liquid rich in zinc-ammonia complex stored in the storage tank enters a closed ammonia evaporation tank through a pipeline and is evaporated by directly heating steam, when the temperature reaches above 90 ℃, ammonia is decomposed from the zinc-ammonia complex, and the chemical reaction is simply as follows:
3Zn(NH 3 )4CO 3 +4H 2 O=12NH 3 +2CO 2 ·ZnCO 3 ·Zn(OH) 2 +2CO 2 ↑
after the wastewater generated by slurry rinsing enters a rinsing wastewater pool and a part of the wastewater is used for cleaning leaching residues, the washing wastewater enters an ammonia absorption tower to be concentrated by ammonia absorption liquid and then returns to the leaching process.
The calcination reaction is simple: ZnCO 3 ·Zn(OH) 2 ·H 2 O =3ZnO+CO 2 ↑+3H 2 O↑
Furthermore, the zinc content of the zinc hypoxide is less than or equal to 14%.
Further, the step of removing and purifying is to add a mixture of copper sulfate pentahydrate and zinc powder into the zinc oxide leachate at normal temperature, control the pH to be 3.5-4, and stir for 2-3 hours; the simple substances Cu and Cu exist in the solution at the same time 2+ Controlling certain conditions to form CuCl precipitate; adding excessive Zn powder after solid-liquid separation for reacting for 45-50 min, then carrying out solid-liquid separation, and then reacting with KMnO with the concentration of 10wt% 4 、1.5wt%Fe 2 (SO 4 ) 3 The solution is mixed according to the ratio of 1000: 1 toReacting at the volume ratio of 4: 5-10 at 40-70 ℃ for 40-50 min, and performing solid-liquid separation to obtain the ammonia leaching purification solution.
Further, the precipitator is polymeric ferric sulfate, and is added according to the dosage proportion of 10.6-32 g/5L of ammonia leaching purification liquid by volume. Fe (H) 2 O) 5 H 2 O 3+ +F-=Fe(H 2 O)5F 2+ +H 2 O。
The invention has the beneficial effects that:
the method has the advantages of high zinc leaching efficiency in the secondary zinc oxide, improvement of the recovery rate of zinc, removal of metal impurities, fluorine and chlorine, removal rate of fluorine and chlorine of 85 percent, achievement of the requirement of safe production, low external discharge of wastewater, improvement of comprehensive recovery rate, improvement of the economic benefit of the clean production level and remarkable environmental benefit. Dimer and high polymer exist in the polyferric sulfate liquid, and polynuclear ions with high valence positive charges have strong attraction to fluorine, are easy to agglomerate into large floccules and are easy to precipitate. Production of Fe (OH) 3 Precipitate, less fluorine and chlorine content, and less harmful elements such as copper, manganese, lead, cadmium, etc.
Compared with the prior art, the invention has the following advantages:
the preparation method of the active zinc oxide disclosed by the invention has the advantages of short process flow, strong equipment universality and low investment, and the leaching solution ammonia water can be recycled. It uses the zinc-containing period road ash of smelting plant as main raw material, and has the advantages of low cost, simple impurity-removing process, short flow, recyclable ammonia water and strong raw material adaptability.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Firstly, preparing raw materials such as zinc hypoxide, ammonia-ammonium liquid and the like; the second step, ammonia-ammonium leaching: adding the zinc hypoxide as raw material into a 2.4m 2.5m leaching tank sealed with ammonia-ammonium solution to obtain the product [ CO ] 2 ]And [ NH ] 3 ]The molar concentration ratio of the raw materials is 1: 4, the raw materials are prepared by adding water into concentrated ammonia water and ammonium carbonate, the total ammonia concentration of the raw materials to the zinc hypoxide is 6mol/L, and the raw materials are leachedThe temperature is 40 ℃; the liquid-solid ratio L: S =3:1, and the leaching time is 2 h; performing pressure filtration on the leaching slurry by an ammonia-ammonium liquid leaching source X400 pressure filter to perform liquid-solid separation to obtain a zinc oxide leaching solution, separating zinc into a filtered liquid phase, leaving other components such as Pb, Mg, SiO2, S, C and the like in filter residues to obtain leaching residues, wherein the leaching residues contain more water-soluble zinc, collecting the part of residues into a residue washing tank, rinsing the part of leaching residues by using rinsing wastewater generated in the following process for 2 times, performing pressure filtration, and returning the washing water to the ammonia-ammonium leaching process after passing through an ammonia absorption tower; step three, impurity removal and purification: adding 1.4 parts of mixture of copper sulfate pentahydrate and zinc powder in a mass ratio of 1: 2 into 100 parts of zinc oxide leachate at normal temperature, controlling the pH to be 3.5, stirring for 2 hours, adding excessive Zn powder after solid-liquid separation for reacting for 50min, then performing solid-liquid separation, and then mixing with 10wt% KMnO 4 、1.5wt%Fe 2 (SO 4 ) 3 The solution reacts for 40min at 40 ℃ according to the volume ratio of 1000: 4: 5, and ammonia leaching purification solution is obtained after solid-liquid separation; step four, precipitation: adding the precipitator into the ammonia leaching purification solution according to the dosage proportion of 10.6g/5L of the ammonia leaching purification solution by volume, stirring and reacting at normal temperature for 30min, standing for 10min, and performing liquid-solid separation to obtain zinc-ammonium double salt intermediate slurry; step five, pyrolysis ammonia distillation: feeding zinc ammonium double salt intermediate slurry stored in a storage tank into a closed ammonia steaming tank through a pipeline, directly heating by steam for ammonia steaming, keeping the temperature at 90 ℃ for 0.5h, rinsing and filter pressing the slurry, feeding the slurry into a rinsing tank for rinsing, wherein water for rinsing is fresh tap water, the rinsing frequency is 1, performing solid-liquid separation, feeding rinsing wastewater into the second step for cleaning leached residues, drying the filtered residues by using an SKSZ125 flash evaporation dryer after filter pressing, and dehydrating and drying wet materials to ensure that the water content is less than 0.5%; sixth step, calcining: and (3) feeding the dried material into a SKDS80 calciner for calcining at 550 ℃ for 2.5 hours to obtain the zinc oxide. The main components of the secondary zinc oxide used in example 1 are shown in table 1.
Table 1 main components of zinc hypoxide used in example 1
Example 2
Firstly, preparing raw materials such as zinc hypoxide, ammonia-ammonium liquid and the like; the second step, ammonia-ammonium leaching: adding the zinc hypoxide as raw material into a 2.4m 2.5m leaching tank sealed with ammonia-ammonium solution to obtain the product [ CO ] 2 ]And [ NH ] 3 ]The molar concentration ratio of the raw materials is 1: 3, the raw materials are prepared by adding water into concentrated ammonia water, ammonium carbonate or ammonium bicarbonate, the total ammonia concentration is 3mol/L relative to the zinc hypoxide, and the leaching temperature is 40 ℃; the liquid-solid ratio L: S =3:1, and the leaching time is 1 h; performing pressure filtration on the leaching slurry by an ammonia-ammonium liquid leaching source X400 pressure filter to perform liquid-solid separation to obtain a zinc oxide leaching solution, separating zinc into a filtered liquid phase, leaving other components such as Pb, Mg, SiO2, S, C and the like in filter residues to obtain leaching residues, wherein the leaching residues contain more water-soluble zinc, collecting the part of residues into a residue washing tank, rinsing the part of leaching residues by using rinsing wastewater generated in the following process for 2 times, performing pressure filtration, and returning the washing water to the ammonia-ammonium leaching process after passing through an ammonia absorption tower; step three, impurity removal and purification: adding 1.4 parts of mixture of copper sulfate pentahydrate and zinc powder in a mass ratio of 1: 2 into 100 parts of zinc oxide leachate at normal temperature, controlling the pH to be 3.5, stirring for 2 hours, adding excessive Zn powder after solid-liquid separation for reacting for 50min, then performing solid-liquid separation, and then mixing with 10wt% KMnO 4 、1.5wt%Fe 2 (SO 4 ) 3 The solution reacts for 50min at 70 ℃ according to the volume ratio of 1000: 4: 10, and ammonia leaching purification solution is obtained after solid-liquid separation; step four, precipitation: adding the precipitant into the ammonia leaching purification solution according to the dosage proportion of 32g/5L of the precipitant in terms of ammonia leaching purification solution volume, stirring and reacting at normal temperature for 50min, standing for 20min, and performing liquid-solid separation to obtain zinc-ammonium double salt intermediate slurry; step five, pyrolysis ammonia distillation: feeding zinc ammonium double salt intermediate slurry stored in a storage tank into a closed ammonia steaming tank through a pipeline, directly heating by steam for ammonia steaming, keeping the temperature at 100 ℃ for 1h, rinsing and filter pressing the slurry, feeding the slurry into a rinsing tank for rinsing, wherein the rinsing water is fresh tap water, the rinsing times are 2 times, performing solid-liquid separation, and feeding the rinsing wastewater to the second step for cleaning leaching residues, and pressingDrying the filtered filter cake by using a SKSZ125 flash evaporation dryer, and dehydrating and drying the moisture-containing material to ensure that the moisture content is less than 0.5%; sixthly, calcining: and (3) calcining the dried material in a calcining furnace SKDS80 of Dongda for 3h at 550 ℃ to obtain the zinc oxide. The secondary zinc oxide of example 2 was the same as example 1.
The active zinc oxides of example 1 and example 2 were subjected to performance tests, and the test results are shown in Table 2
Table 2 results of performance test of activated zinc oxide of example 1 and example 2
Note: reference is made to HG/T2572-2020 active zinc oxide.
Claims (5)
1. A preparation method of active zinc oxide is characterized in that zinc hypoxide is used as a raw material, zinc oxide leachate is obtained by ammonia-ammonium liquid leaching, and ammonia leaching purification liquid is obtained by continuous impurity removal and purification; adding a precipitator into the ammonia leaching purification solution, stirring and reacting at normal temperature for 30-50 min, standing for 10-20 min, performing liquid-solid separation to obtain zinc ammonium double salt intermediate slurry, performing pyrolysis ammonia distillation and slurry rinsing and filter pressing, allowing the slurry to enter a rinsing tank for rinsing, wherein rinsing water is fresh tap water, the rinsing times are 1-2 times, performing solid-liquid separation, drying a filter cake after filter pressing, dehydrating and drying a wet material, and calcining the dried material in a calcining furnace at 550 ℃ for 2.5-3 h to obtain high-purity zinc oxide.
2. The method for preparing active zinc oxide according to claim 1, wherein the ammonia-ammonium solution is prepared by adding water to concentrated ammonia water, ammonium carbonate or ammonium bicarbonate, the total ammonia concentration of the ammonia-ammonium solution is 3-6 mol/L relative to zinc hypoxide, and the leaching temperature is 40 ℃; the liquid-solid ratio L: S =3:1, and the leaching time is 1-2 h.
3. The method of claim 1, wherein the zinc content of the zinc hypoxide is less than or equal to 14%.
4. The method for preparing active zinc oxide according to claim 1, wherein the impurity removal and purification comprises: adding 1.4-1.6 parts of mixture of copper sulfate pentahydrate and zinc powder according to the mass ratio of 1: 1-2 into 100 parts of zinc oxide leachate at normal temperature, controlling the pH to be 3.5-4, stirring for 2-3 h, adding excessive Zn powder after solid-liquid separation, reacting for 45-50 min, performing solid-liquid separation, and then mixing with 10wt% KMnO 4 、1.5wt%Fe 2 (SO 4 ) 3 The solution reacts for 40-50 min at 40-70 ℃ according to the volume ratio of 1000: 1-4: 5-10, and ammonia leaching purification solution is obtained after solid-liquid separation.
5. The method for preparing active zinc oxide according to claim 1, wherein the precipitant is polymeric ferric sulfate, and the precipitant is added in an amount of 10.6-32 g/5L based on the volume of the ammonia leaching purification solution.
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| CN102583503A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Method for preparing activated zinc oxide by utilizing high-arsenic secondary zinc oxide resource ammonia-ammonium process |
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| US20150246822A1 (en) * | 2012-09-25 | 2015-09-03 | Sichuan Xinhong Technology Co., Ltd. | Method for Producing a High-purity Nanometer Zinc Oxide from Electrolytic Zinc Acid Leaching Residues by Ammonia Decarburization |
| US20150252446A1 (en) * | 2012-09-25 | 2015-09-10 | Juhong Technology Co., Ltd. | Method for Producing a High-purity Nanometer Zinc Oxide from Steel Plant Smoke and Dust by Ammonia Decarburization |
| CN106115768A (en) * | 2015-10-05 | 2016-11-16 | 李果 | A kind of comprehensive cyclic utilization method of steel plant zinc smoke ash |
| CN113830819A (en) * | 2021-10-20 | 2021-12-24 | 安徽锦华氧化锌有限公司 | Preparation method of skin-color zinc oxide |
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| CN102583503A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Method for preparing activated zinc oxide by utilizing high-arsenic secondary zinc oxide resource ammonia-ammonium process |
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