CN102828035B - Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process - Google Patents
Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process Download PDFInfo
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- CN102828035B CN102828035B CN201210358125.2A CN201210358125A CN102828035B CN 102828035 B CN102828035 B CN 102828035B CN 201210358125 A CN201210358125 A CN 201210358125A CN 102828035 B CN102828035 B CN 102828035B
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- acid leaching
- ammonia
- zinc
- leaching slag
- zinc oxide
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 117
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000002386 leaching Methods 0.000 title claims abstract description 115
- 239000011701 zinc Substances 0.000 title claims abstract description 106
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 89
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 83
- 230000008569 process Effects 0.000 title claims abstract description 82
- 239000002253 acid Substances 0.000 title claims abstract description 60
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 58
- 239000002893 slag Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000005262 decarbonization Methods 0.000 title abstract 4
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 34
- 238000005261 decarburization Methods 0.000 claims description 28
- 239000012530 fluid Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 11
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 11
- 239000004571 lime Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 abstract description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- KKTCWAXMXADOBB-UHFFFAOYSA-N azanium;hydrogen carbonate;hydrate Chemical compound [NH4+].O.OC([O-])=O KKTCWAXMXADOBB-UHFFFAOYSA-N 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 abstract 1
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 16
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 14
- 229940007718 zinc hydroxide Drugs 0.000 description 14
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- -1 papermaking Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- DNGCSGDMYSRLAR-UHFFFAOYSA-N [C+4].N.N Chemical compound [C+4].N.N DNGCSGDMYSRLAR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel 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
- GUSDBSJBSRXHFX-UHFFFAOYSA-L zinc;azane;sulfate Chemical compound N.[Zn+2].[O-]S([O-])(=O)=O GUSDBSJBSRXHFX-UHFFFAOYSA-L 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting an ammonia process. When the electrolytic zinc acid leaching slag to be treated is leached, 0.3-0.5kg of sodium fluosilicate is added into per cubic meter of ammonia water-ammonium bicarbonate solution, 30-60kg of slaked lime is added into per cubic meter of leaching liquid after leaching, decarbonization reaction is carried out, the ammonia process is applied to treatment on the electrolytic zinc acid leaching slag, and adaptability improvement is carried out on the existing ammonia process; and a decarbonization step is added after a leaching step, and sodium fluosilicate, a surface active agent and dicyanodiamine are added while leaching, on the one hand, the zinc in the electrolytic zinc acid leaching slag is fully recycled; on the other hand, zinc oxide with larger specific surface area can be obtained, and purity of the obtained zinc oxide can reach up to 99.7%, thus the method disclosed by the invention has higher economic value; besides, the method disclosed by the invention has low energy consumption and high efficiency, the treated electrolytic zinc acid leaching slag is changed into general waste from the electrolytic zinc acid leaching slag which is taken as high-risk waste, and the effects of being economic and environment-friendly can be achieved.
Description
Technical field
The present invention relates to a kind of production method of zinc oxide, particularly a kind of production method of high pure zinc oxide.
Background technology
Zinc hydrometallurgy mainly adopts the production technique of roasting-leaching-electrolysis at present, in the electrolytic zinc acid leaching slag of discharge, zinc content is counted in mass ratio and is generally 6-9%, what have can reach 20%, and the material phase analysis that acid leaching residue is done and X diffraction analysis show, in leached mud, zinc is mainly with ZnFe
2o
4form exists, meanwhile, the content 6-12% of sulphur, wherein sulfate radical content is 15-30%, ore deposit, various places calcium, magnesium salts content difference also contain Cu simultaneously
2+, Pb
2+, Cd
2+, Ni
2+, Hg
2+, As
3+or As
5+plasma, its roughly mass content be about: copper 1%, plumbous 0.8%, iron 4%, silicon 3%, arsenic 0.3%, silver 0.003%, calcium 12%, magnesium 3%).In order to reclaim these zinc, current treatment process has two kinds of pyrogenic process and wet methods, and pyrogenic process is rotary kiln evaporation method (waelz process) and fuming furnace volatilization method, as the publication number Chinese patent application that is CN101886180.Wet method has hot acid to leach or high-temperature pressurizing leaches.Pyrogenic attack technical process is long, and maintenance of equipment amount is large, invests highly, and Working environment is poor, need to consume a large amount of coal-fired or metallurgical coking coal, and benefit is low, and environmental pollution is large.Therefore conventionally leach with hot acid or high pressure leaching, these methods still existent defect are: 1. consume a large amount of acid, 2. the pressure of deironing is large, need to consume more reagent, 3. high-temperature high-pressure apparatus seriously corroded, and the complicated investment of equipment is larger; 4. running cost is high, deficiency in economic performance.5. last slag of discharging is acid slag, brings new pollution to environment, have to take solidify & bury, not only contaminate environment, and waste resource.
Optimal method is that the selectivity of carrying out zinc leaches, and zinc is entered in solution, and zinc obtains valuable recycling.
On the other hand, the quality percentage composition that high pure zinc oxide generally refers to zinc oxide is 99.7% and above zinc oxide product, high-purity zinc oxide is the indispensable a kind of high-tech functional material of modern industry, of many uses, be mainly used in the tens of kinds of industry and enterprises such as glass, feed, pottery, dyestuff, paint, papermaking, rubber, agricultural chemicals, oil refining, zinc-plated, special steel material, alloy, science and techniques of defence, no matter be glass, papermaking, or rubber, oil refining etc. are all in great demand to zinc oxide, and purity requirement is very high.
Produce at present the method for high-purity zinc oxide, it is mainly indirect method, indirect method is generally take zinc ingot metal as raw material, pass through electrolytic reduction, or high-temperature gasification, atmospheric oxidation again condensation collection makes zinc oxide, different zinc ingot metal raw materials, the zinc oxide purity of producing is also different, and this technique is mainly produced the zinc oxide of 99.5%--99.7%.
Ammonia process is a kind of common method of preparing zinc oxide, the general step of ammonia process (ammonia-carbon ammonium associating lixiviation process is produced zinc oxide) comprising at present: ammonia-carbon ammonium is leach liquor, material containing zinc is leached, and zinc ammonia element complex liquid makes zinc oxide product through purification, ammonia still process crystallization, drying and calcining.
This traditional ammonia process is prepared zinc oxide and is never applied to the processing of electrolytic zinc acid leaching slag, and major cause is:
1) in electrolytic zinc acid leaching slag, have a large amount of calcium sulfate parcels and make zinc wherein leach difficulty, the rate of recovery is low
2) in electrolytic zinc acid leaching slag, contain the sulfate radical of 15-30%, a large amount of ammonia are converted into ammonium sulfate, and ammonia consumption is high
3) by the zinc ammonia complex liquid direct purification after leaching, owing to still there is a large amount of free ammonias in liquid, impurity complexing power is strong, purifies and is difficult to thoroughly, finally affect the purity of zinc oxide product.
4) owing to there is a large amount of sulfate radicals in solution, in ammonia still process process, will separate out part of sulfuric acid zinc ammonium double salt, affect zinc oxide purity.
In addition, ammonia leaching process is produced zinc oxide at present, xln is zinc subcarbonate, then calcine, for obtaining high purity product, need for maintaining the sufficiently high decomposition temperature of zinc subcarbonate, general temperature is more than 500 ℃, as the Chinese patent application that application number is 200610130477.7, high-temperature calcination will have influence on the specific surface area of zinc oxide, affects the activity of zinc oxide product.
In sum, for the processing of electrolytic zinc acid leaching slag, how in the tailings of low zinc content and the material of high impurity content, effectively to leach zinc wherein, and obtain highly purified zinc oxide, overcome traditional pyrogenic process and the shortcoming of wet method simultaneously, become industry technical barrier urgently to be resolved hurrily and unsolved.
Summary of the invention
One of goal of the invention of the present invention is: for the problem of above-mentioned existence, the zinc in a kind of efficient recovery electrolytic zinc acid leaching slag is provided and prepares the method for high pure zinc oxide.
The technical solution adopted in the present invention is: a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide, comprises the following steps successively:
Leach pending electrolytic zinc acid leaching slag, purification and impurity removal, ammonia still process crystallization and drying and calcining, it is characterized in that:
Leach pending electrolytic zinc acid leaching slag, when leaching, leach with ammoniacal liquor-ammonium fluid; Wherein, NH
3volumetric molar concentration be 5-6mol/L, CO
2volumetric molar concentration be 0.85-1.0 mol/L, and in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
After leaching, the decarburization that heats up, its method is: in every cubic metre of leaching liquid, add 30-60kg white lime, carry out decarburizing reaction, temperature of reaction is more than 60 ℃, controls CO
3 2-concentration≤0.3mol/L, then filtering separation.
Purification and impurity removal, ammonia still process crystallization and drying and calcining step all adopt current common ammonia process to prepare the processing parameter of zinc oxide.
Obtain highly purified zinc oxide, first need to guarantee that the zinc in electrolytic zinc acid leaching slag can leach as much as possible, can improve so on the one hand the rate of recovery of zinc, on the other hand, in leach liquor, the content of zinc is larger, foreign matter content is also just less, and guarantee makes more highly purified zinc oxide under equal processing condition.
The technology that first the present invention prepares existing ammonia process zinc oxide is applied to the processing to electrolytic zinc acid leaching slag, meanwhile, on the technique basis of existing ammonia process, in leaching liquid, adds appropriate Sodium Silicofluoride; And increase the step of decarburization.
Owing to containing a large amount of calcium sulfate (15-30%) in electrolytic zinc acid leaching slag, calcium sulfate is to metal oxide skinning buffer actions such as zinc oxide, cause acid environment to be difficult to leach, so the present invention adopts ammonia process to leach, under the effect of ammonia-carbon ammonium associating liquid, calcium sulfate is converted into calcium carbonate and calcium hydroxide, in switching process, realizes successively peeling off with zinc ammino contract of calcium sulfate and walks; But the ultrafine particulates such as calcium hydroxide also play certain inhibition to complexation leaching, in order to address this problem, present inventor draws by great many of experiments: appropriate silicofluoric acid is received and can be abolished ultrafine particulate to containing zinc particle package action, realize ultrafine particulate layering floating, thereby zinc is exposed and is immersed in liquid.
Decarburization is fallen in ammonia process and is added ammonium persulphate as oxygenant.
Increase decarburization and fall ammonia step, can eliminate too much free ammonia on the one hand, reduce the complex ability of foreign ion, foreign ion is removed, be beneficial to raising depuration quality, reduce and purify drug dosage; Can remove on the other hand carbanion in solution, make to be conducive to obtain the presoma zinc hydroxide that crystalline core size is less, decomposition temperature is lower in the follow-up deamination hydrolytic process of complex liquid and precipitate.
Meanwhile, present inventor draws by great many of experiments:, can provide on the one hand and replace CO as decarburizer with white lime
3 2-ligand OH
-, make CO
3 2-eliminate and form CaCO
3precipitation, slightly strong alkaline environment contributes to the ferrous metallic impurity precipitation that waits in addition, for follow-up purification creates conditions.On the other hand, white lime is inexpensive.
Wherein:
The chemical equation of leaching step is:
ZnO+nNH
3 +H
2O→［Zn(NH
3)n］
2++2OH
-
ZnFe
2O
4 +nNH
3+4H
2O→［Zn(NH
3)n］
2++2Fe(OH)
3 ↓+2OH
-
ZnFe
2O
4 +nNH
3+H
2O→［Zn(NH
3)n］
2++Fe
2O
3↓+2OH
-
Zn
2SiO
4 +2nNH
3→ 2［Zn(NH
3)n］
2+ + SiO
4 4-
Zn(OH)
2 +nNH
3 →［Zn(NH
3)n］
2++2OH
-
Zn+nNH
3 +2H
2O→［Zn(NH
3)n］
2++H
2+2OH
-
ZnSO
4+nNH
3→［Zn(NH
3)n］
2++SO
4 2-
Wherein n=1～4;
Chemical reaction in decarbonation process is:
Ca(OH)
2﹦ Ca
2+ +2OH
-
Ca
2++ CO
3 2-→CaCO
3↓
NH
3H
2O + NH
4HCO
3→ 2NH
3↑ +CO
2↑ +2H
2O
The reaction occurring in purification and impurity removal process:
S
2O
8 2-+ Mn
2++ 2NH
3·H
2O + H
2O→ Mn O（OH）
2↓ + 2NH
4 ++2SO
4 2-+ 2H
+
S
2O
8 2-+2Fe
2+ +6H
2O →2SO
4 2-+ 2Fe(OH)
3↓+ 6H
+
AsO
4 3- + Fe
3- → FeAsO
4↓
AsO
3 3- + S
2O
8 2-+ H
2O → 2SO
4 2- + AsO
4 3-+ 2H
+
2H
3AsO
3 + 8Fe(OH)
3 → (Fe
2O
3)
4As
2O
3·5H
2O↓ +10H
2O
M
2++ S
2→ MS ↓ M represents Cu
2+, Pb
2+, Cd
2+, Ni
2+hg
2+plasma
As
3+ + S
2-→As
2S
3↓
Y
2++ Zn → Zn
2+wherein Y representative of+Y: Cu
2+, Pb
2+, Cd
2+, Ni
2+plasma;
The reaction equation of ammonia still process step:
［Zn(NH
3)
i］
2++2OH
-= Zn(OH)
2↓+ iNH
3↑ i =1～4
［Zn(NH
3)
4］CO
3 +H
2O→ Zn(OH)
2↓+ CO
2↑ + 4NH
3↑；
The chemical equation of drying and calcining:
Zn(OH)
2→ZnO + H
2O↑
As preferably: while leaching pending electrolytic zinc acid leaching slag, be also added with the Dicyanodiamide of 0.5-1kg and the tensio-active agent of 0.03-0.05kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
Tensio-active agent and Sodium Silicofluoride mating reaction are played the ultrafine particulates such as calcium hydroxide are disperseed, peel off effect.Improve the rate of recovery of zinc, thereby the relative concentration that improves zinc in leaching liquid is more conducive to the preparation of high pure zinc oxide.
As preferably: the Dicyanodiamide that is also added with 0.5-1kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
Dicyanodiamide, as ammonia stablizer, can reduce the volatilization of ammonia in leaching process, improves leaching Working environment, reduces the loss of ammonia.
As preferably: in the time of the pending electrolytic zinc acid leaching slag of leaching, carry out ball milling leaching simultaneously.
Utilize ball milling leaching, destroy the parcel of ultrafine particulate to zinc by mechanical force, can improve leaching velocity and leaching yield.
As preferably: add 3-4kg ammonium persulphate when decarburization in every cubic metre of aforementioned liquids.
As preferably: after decarbonation process, in solution, add appropriate Neutral ammonium fluoride deliming, add-on be calcium ion theoretical value in solution 1.5-2 doubly;
As preferably: add sodium sulphite to sink zinc in the waste liquid after ammonia still process crystallization, obtain zinc sulphide filter cake and liquid portion after separation; Add white lime to obtain mixed solution at liquid portion, in whipping process, add tensio-active agent; Mixed solution is carried out to ammonia still process crystallization, and Tc, for not higher than 105 ℃, stirs in ammonia still process process, and stirring velocity is 300-500 rev/min, and the ammonia of effusion, by cooling recovery, obtains calcium sulfate powder and carries out rinsing, dry, obtains calcium sulfate product.
Like this, on the one hand the zinc not being utilized in crystal waste is further recycled and obtained zinc sulphide; Can reclaim on the other hand ammonia recycling, soak etc. for ammonia, cost-saving, be beneficial to environmental protection.
Due to technical scheme of the present invention, after ammonia still process crystallisation step, the xln obtaining is mainly zinc hydroxide, the decomposition temperature of zinc hydroxide is lower than zinc carbonate, adopt the temperature of 150-300 ℃ to calcine, can obtain purity 99.7% and the zinc oxide product of above and bigger serface, specific surface area is generally at 80m/g
2above.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows: ammonia process is applied to the processing to electrolysis acid leaching residue, and existing ammonia process is carried out to adaptation, after leaching, increase decarbonation process and in the time of leaching, added Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, the zinc that makes on the one hand electrolytic zinc acid leaching slag fast, as far as possible fully leach, is fully recycled the zinc in electrolytic zinc acid leaching slag; On the other hand, the present invention preferably adopts lower calcining temperature, can obtain can reaching more than 99.7% compared with the zinc oxide while purity of bigger serface, has very high economic worth; In addition, treatment process energy consumption of the present invention is low, efficiency is high, treated electrolytic zinc acid leaching slag, (sulfate radical is recycled by-product calcium sulfate powder to become general waste from the electrolytic zinc acid leaching slag as high-risk waste (due to a large amount of acid group of content and soluble heavy metal), other heavy metals are recycled in removal of impurities process), reach the effect of economic environmental protection.
Embodiment
The present invention is described in detail below.
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1:
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity zinc oxide, comprise the following steps successively:
(1) leaching: get 500 grams of electrolytic zinc acid leaching slags (wherein, by quality ratio, containing zinc 8.6%, copper 1.03%, calcium sulfate 32%, cadmium 0.05%, arsenic 0.03%), be milled to 200 orders; Produce 1500ml ammoniacal liquor-ammonium fluid as ammonia leaching solution, wherein NH
3concentration is 6mol/L, CO
2concentration is 1mol/L, in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.3kg Sodium Silicofluoride, electrolytic zinc acid leaching slag joins and in above-mentioned ammonia leaching solution, carries out three sections of leachings, each section of leaching time is 2 hours, after solid-liquid separation, 38.7 grams, zinc (zinc recovery 90.1%) in gained zinc ammonia complex liquid, 41.72 grams of sulfate radicals in zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: add 30kg white lime in the decarbonizer of belt stirrer in every cubic metre of leaching liquid, indirect heating to 60 ℃, works as CO
3 2-when concentration=0.28mol/L, carry out solid-liquid separation;
(3) purification and impurity removal: add 0.5 gram of sodium sulphite in the liquid after (2) step solid-liquid separation, stir after 2 hours and filter, add 0.2 gram of potassium permanganate, stir after 2 hours and filter;
(4) ammonia still process crystallization: the zinc ammonia complex liquid after purifying is filtered to post-heating ammonia still process, and ammonia distiller stirring velocity per minute 600 turns, and stops ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(5) in the filtrate after ammonia still process crystallization, add sodium sulphite to sink zinc, after reaction, separate and obtain zinc sulphide filter cake and solution; Add white lime in solution part, and stir obtain mixed solution, in whipping process, add tensio-active agent; Mixed solution is carried out to ammonia still process conversion and make ammonium sulfate be converted into calcium sulfate powder, ammonia still process temperature, for not higher than 105 ℃, stirs in ammonia still process process, stirring velocity is 300 revs/min, the ammonia of overflowing is by cooling recovery, and calcium sulfate powder carries out rinsing, dry, obtains calcium sulfate powder product;
(6) drying and calcining: the zinc hydroxide filter cake after filtration adds respectively the deionized water of 200ml to carry out three washings, adding 0.05 gram of sodium lauryl sulphate in washing process for the first time, the zinc hydroxide filter cake after press filtration is put into retort furnace 300 degree calcining 3 hours.
The zinc oxide quality percentage composition of gained is 99.7%, specific surface area 80m
2/ g.
Embodiment 2
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity zinc oxide, comprise the following steps successively:
(1) leaching: get 500 grams of electrolytic zinc acid leaching slags (wherein, by quality ratio, containing zinc 9.2%, copper 1.13%, calcium sulfate 30%, cadmium 0.056%, arsenic 0.031%); Produce 1500ml ammoniacal liquor-ammonium fluid as ammonia leaching solution, wherein NH
3concentration is 5mol/L, CO
2concentration is 0.85mol/L, in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.5kg Sodium Silicofluoride, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the surfactant SDS of 0.04kg, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the Dicyanodiamide of 0.8kg, electrolytic zinc acid leaching slag joins and in above-mentioned ammonia leaching solution, carries out three sections of leachings, ball milling simultaneously, each section of leaching time is 2.5 hours, after solid-liquid separation, 41.9 grams, zinc (zinc recovery 91.2%) in gained zinc ammonia complex liquid, 58.2 grams of sulfate radicals in zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: add 60kg white lime in the decarbonizer of belt stirrer in every cubic metre of leaching liquid, indirect heating to 90 ℃, works as CO
3 2-when concentration=0.26mol/L, discharge mixed solution and add 4kg ammonium persulphate to stir by every cubic metre, continue decarburization oxidation except de-iron, manganese etc., treat CO
3 2-when=0.04mol/L, carry out solid-liquid separation, the time of whole stirring decarburization is 12 hours again;
(3) purification and impurity removal: add 0.56 gram of sodium sulphite in the liquid after (2) step solid-liquid separation, stir after 2 hours and filter, add 0.2 gram of potassium permanganate, stir after 2 hours and filter;
(4) ammonia still process crystallization: the zinc ammonia complex liquid after purifying is filtered to post-heating ammonia still process, and ammonia distiller stirring velocity per minute 600 turns, and stops ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(5) drying and calcining: the zinc hydroxide filter cake after filtration adds respectively the deionized water of 200ml to carry out three washings, adding 0.05 gram of sodium lauryl sulphate in washing process for the first time, the zinc hydroxide filter cake after press filtration is put into retort furnace 150 degree calcining 4.2 hours.
The flat quality percentage composition of zinc oxide of gained is 99.85%, specific surface area 86m
2/ g.
Embodiment 3
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity zinc oxide, comprise the following steps successively:
(1) leaching: get 1500 grams of acid leaching residues (zinc 9.0%, copper 0.80%, calcium sulfate 30%, cadmium 0.040%, arsenic 0.25%, silicon 3%, arsenic 0.3%, silver 0.003%, magnesium 3%); Produce 1500ml ammoniacal liquor-ammonium fluid as ammonia leaching solution, wherein NH
3concentration is 5mol/L, CO
2concentration is 0.95mol/L, in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.3kg Sodium Silicofluoride, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the surfactant SDS of 0.05kg, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the Dicyanodiamide of 0.5kg, electrolytic zinc acid leaching slag joins and in above-mentioned ammonia leaching solution, carries out three sections of leachings, ball milling simultaneously, each section of leaching time is 3.0 hours, after solid-liquid separation, obtain leaching liquid, 123.66 grams, zinc (zinc recovery 91.6%) in gained zinc ammonia complex liquid, 165.0 grams of sulfate radicals in zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: add 55kg white lime in the decarbonizer of belt stirrer in every cubic metre of leaching liquid, indirect heating to 95 ℃, works as CO
3 2-when concentration=0.3mol/L, discharge mixed solution and add 3.5kg ammonium persulphate to stir by every cubic metre, continue decarburization oxidation except de-iron, manganese etc., treat CO
3 2-when=0.04mol/L, carry out again solid-liquid separation;
(3) purification and impurity removal: add 1.56 grams of sodium sulphite in the liquid after (2) step solid-liquid separation, stir after 2 hours and filter, add 0.5 gram of potassium permanganate, stir after 2.5 hours and filter;
(4) ammonia still process crystallization: the zinc ammonia complex liquid after purifying is filtered to post-heating ammonia still process, stop ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(5) drying and calcining: the zinc hydroxide filter cake after filtration adds respectively the deionized water of 600ml to carry out three washings, in washing process for the first time, add the sodium lauryl sulphate of 0.12 gram/cubic metre, the zinc hydroxide filter cake after press filtration is put into retort furnace 280 degree calcining 3.8 hours.
The zinc oxide quality percentage composition of gained is 99.75%, specific surface area 92m
2/ g.
Embodiment 4
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity zinc oxide, comprise the following steps successively:
(1) leaching: 120 tons of raw materials, come from Yunnan Chihong Zinc & Germanium Co., Ltd.'s Huize and smelt the acid leaching residue that old factory many decades accumulates, zinc 11.2%, copper 0.91%, lead 1.3%, acid group 27.6%, cadmium 0.03% in raw material;
Produce 360 cubic metres of ammoniacal liquor-ammonium fluids as ammonia leaching solution, wherein NH
3concentration is 5.5mol/L, CO
2concentration is 0.90mol/L, in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.36kg Sodium Silicofluoride, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the surfactant SDS of 0.045kg, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the Dicyanodiamide of 0.42kg, electrolytic zinc acid leaching slag joins and in above-mentioned ammonia leaching solution, carries out three sections of leachings, ball milling simultaneously, each section of leaching time is 3.5 hours, after solid-liquid separation, obtain leaching liquid, 12.1 tons, zinc (zinc recovery 90.0%) in gained zinc ammonia complex liquid, 13.6 tons of sulfate radicals in zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: add 56kg white lime in the decarbonizer of belt stirrer in every cubic metre of leaching liquid, indirect heating to 97 ℃, works as CO
3 2-when concentration=0.26mol/L, discharge mixed solution and add 3.6kg ammonium persulphate to stir by every cubic metre, continue decarburization oxidation except de-iron, manganese etc., treat CO
3 2-when=0.04mol/L, carry out again solid-liquid separation;
(3) purification and impurity removal: add 1.5kg sodium sulphite at every cubic metre of zinc ammonia complex liquid, stir after 2 hours and filter, every cubic metre of zinc ammonia complex liquid adds 0.3kg potassium permanganate;
(4) ammonia still process crystallization: the zinc ammonia complex liquid after purifying is filtered to post-heating ammonia still process, and ammonia distiller stirring velocity per minute 580 turns, and stops ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(5) drying and calcining: the ion exchanged water that the filter cake after filtration adds by liquid-solid ratio 5:1 carries out three washings, adding 1.25 grams of sodium lauryl sulphate in washing process for the first time, the zinc hydroxide filter cake after press filtration is put into retort furnace 160 degree and is calcined 2 hours.
The zinc oxide quality percentage composition of gained is 99.82%, specific surface area 85m
2/ g.
Claims (8)
1. utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce a method for high pure zinc oxide, comprise the following steps:
Leach pending electrolytic zinc acid leaching slag, purification and impurity removal, ammonia still process crystallization and drying and calcining, it is characterized in that:
Leach pending electrolytic zinc acid leaching slag, when leaching, leach with ammoniacal liquor-ammonium fluid; Wherein, NH
3volumetric molar concentration be 5-6mol/L, CO
2volumetric molar concentration be 0.85-1.0 mol/L, and in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
After leaching, the decarburization that heats up, its method is: in every cubic metre of leaching liquid, add 30-60kg white lime, carry out decarburizing reaction, temperature of reaction is more than 60 ℃, controls CO
3 2-concentration≤0.3mol/L, then filtering separation.
2. a kind ofly according to claim 1 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: while leaching pending electrolytic zinc acid leaching slag, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the tensio-active agent of 0.03-0.05kg.
3. a kind ofly according to claim 2 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: the Dicyanodiamide that is also added with 0.5-1kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
4. a kind ofly according to claim 1 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: in the time of the pending electrolytic zinc acid leaching slag of leaching, utilize ball milling synchronously to leach.
5. a kind ofly according to claim 1 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: when decarburization, in every cubic metre of aforementioned liquids, add 3-4kg ammonium persulphate.
6. a kind ofly according to claim 1 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: after decarbonation process, in liquid, add Neutral ammonium fluoride, the amount adding is Ca in solution
2+the 1.5-2.0 of theoretical value doubly.
7. a kind ofly according to claim 1 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: in the waste liquid after ammonia still process crystallization, add sodium sulphite sink zinc, after reaction, separation obtains zinc sulphide filter cake and solution; Add white lime in solution part, and stir obtain mixed solution, in whipping process, add tensio-active agent; Mixed solution is carried out to ammonia still process conversion and make ammonium sulfate be converted into calcium sulfate powder, ammonia still process temperature, for not higher than 105 ℃, stirs in ammonia still process process, stirring velocity is 300-500 rev/min, the ammonia of overflowing is by cooling recovery, and calcium sulfate powder carries out rinsing, dry, obtains calcium sulfate powder product.
8. a kind ofly according to claim 1 utilize the decarburization of electrolytic zinc acid leaching slag ammonia process to produce the method for high pure zinc oxide, it is characterized in that: the temperature of described drying and calcining is 150-300 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109468A1 (en) * | 1982-11-18 | 1984-05-30 | Extramet | Process for the selective recovery of lead from lead sulphides |
| CN1065685A (en) * | 1992-04-28 | 1992-10-28 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
| CN101538648A (en) * | 2009-03-13 | 2009-09-23 | 昆明理工大学 | Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore |
| CN101886180A (en) * | 2010-07-08 | 2010-11-17 | 陕西理工学院 | Method for preparing high-activity zinc oxide from electrolytic zinc leaching slag and lead smelting granulated slag |
| CN102079537A (en) * | 2009-11-27 | 2011-06-01 | 陕西中科纳米材料股份有限公司 | Preparation method of nano zinc oxide and roasting furnace |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109468A1 (en) * | 1982-11-18 | 1984-05-30 | Extramet | Process for the selective recovery of lead from lead sulphides |
| CN1065685A (en) * | 1992-04-28 | 1992-10-28 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
| CN101538648A (en) * | 2009-03-13 | 2009-09-23 | 昆明理工大学 | Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore |
| CN102079537A (en) * | 2009-11-27 | 2011-06-01 | 陕西中科纳米材料股份有限公司 | Preparation method of nano zinc oxide and roasting furnace |
| CN101886180A (en) * | 2010-07-08 | 2010-11-17 | 陕西理工学院 | Method for preparing high-activity zinc oxide from electrolytic zinc leaching slag and lead smelting granulated slag |
Non-Patent Citations (2)
| Title |
|---|
| 彭清静等.氨浸-碳化法制活性氧化锌.《化工生产与技术》.2001,第8卷(第6期), |
| 氨浸-碳化法制活性氧化锌;彭清静等;《化工生产与技术》;20011231;第8卷(第6期);17 * |
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