CN100417475C - Production of metal zinc powder from zinc dust and zinc dross - Google Patents
Production of metal zinc powder from zinc dust and zinc dross Download PDFInfo
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- CN100417475C CN100417475C CNB2006100246011A CN200610024601A CN100417475C CN 100417475 C CN100417475 C CN 100417475C CN B2006100246011 A CNB2006100246011 A CN B2006100246011A CN 200610024601 A CN200610024601 A CN 200610024601A CN 100417475 C CN100417475 C CN 100417475C
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- Prior art keywords
- zinc
- filtrate
- dross
- zinc powder
- filter residue
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000011701 zinc Substances 0.000 title claims abstract description 113
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 16
- 239000010959 steel Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 26
- 239000002585 base Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000009854 hydrometallurgy Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000011449 brick Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002440 industrial waste Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 29
- 238000005516 engineering process Methods 0.000 description 14
- 239000011133 lead Substances 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 magnesium sulfide sulfides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical group [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 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
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
Images
Abstract
The present invention relates to a method for producing zinc powder from zinc dust and zinc scum, which is a method for producing the zinc powder from the zinc dust of steel works and the zinc scum of zinc smelting plants. Firstly, the zinc dust and the zinc scum are crushed to 0.1 to 1mm, extracted in a strong alkaline solution, stirred at 10 to 100 DEG C for 60 to 100 min and filtered; filter residues are washed with water and used for making bricks or filling land; the filtrate is added with a separating agent 0.5 to 3 times (the mass ratio) of lead content, stirred for 60 min and filtered to get lead filter residues for direct sale. When the filtrate is electrolyzed, first-grade metal zinc powder is deposited and obtained on a cathode. Then, the residual liquid is added with alkali to obtain deposit and filtered; the deposit is added with a slag washing agent and an impurity removing agent, stirred at 10 to 100 DEG C for 30 to 60 min and filtered. The filtrates from the two steps are mixed and returned for alkaline leaching, and then filter residues are filled in land. The present invention has the advantages of simple and tractable process, low cost and no pollution, effectively utilizes industrial waste as resources and has large economic benefit, environmental benefit and social benefit.
Description
Technical field
The present invention relates to a kind of technology of utilizing zinc powder dirt and zinc dross to produce metal zinc, is the method for producing metal zinc as raw material with steel plant's zinc powder dirt and zinc hydrometallurgy factory zinc dross, belongs to the reclamation of solid wastes field.
Background technology
Metal zinc is a kind of important raw material of industry, is mainly used in industries such as metallurgy, chemical industry, pharmacy, battery, and wherein the consumption maximum is coating industry.In the cold galvanizing industry, zinc content in the zinc-rich paint is the 40-70% of this coating gross weight, the surface anticorrosion that is widely used in the metal material in seawater, fresh water and the atmospheric medium protects as the hardware in boats and ships, container, chemical industry, the hydraulic engineering, automobile, motorcycle, bicycle, petroleum pipeline, open-air steel construction piece pylon, bridge steel structure and highway and the metal surface such as to block and all do preservative treatment with zinc-rich paint.In the metal smelt industry, zinc powder can be used for removing beavy metal impurity contained in the raw material, wherein based on the zinc smelting.In the zinc hydrometallurgy process, with contained copper, cobalt, nickel in the zinc dust precipitation zinc solution, impurity such as cadmium, electric zinc per ton need be used the 20-40Kg zinc powder.Supply falls short of demand always for zinc powder, and only global coating industry just surpasses 160,000 t to the annual requirement of zinc powder, and the price of zinc powder also remains on 14000 yuan/t always.Because the fast lifting of world's zinc metallurgy recent decades ability causes zinc consumption of raw materials huge, the zinc metal industry faces no ore deposit can adopt crisis with the raw material supply shortage.Especially China as second-biggest-in-the-world product zinc state, in recent years, all want every year import part raw material to satisfy domestic demand, and import volume was the gesture of growth year by year.Therefore, begin to receive much concern to containing zinc reclamation of waste materials and resource.
Zinc powder dirt is the poisonous solid waste that contains zinc, iron, lead and carbon that is produced in converter and the EAF Steelmaking Process, and the content of zinc is generally 5-40%.Produce the zinc powder dirt that the 1t steel can produce 20-40Kg.At present, the processing method to steel plant's zinc powder dirt mainly contains wet method, pyrogenic process and security landfill.Wet-treating zinc powder dirt mainly is sulfidation roasting, chloridising roasting and acidleach taking technique.Method of roasting has bigger selectivity than acidleach, and zinc is plumbous to be removed more thoroughly, but sulfidation roasting is to ingredient requirement harsh (not containing a large amount of carbon), and sulphur pollution is serious, and it is too high to burn the slag sulfur content, should not be as steel plant's raw material.Chloridising roasting is too serious to the corrosion of equipment, and some factory closes down for this reason.Though acid-hatching of young eggs technology is ripe, the plumbous leaching rate of zinc is lower at normal temperatures and pressures, and unit operations is too much, and leaching agent consumes more, and cost is higher.Thermal process can divide high, medium and low three classes by zinc content, and plasma method, Inred, Wala Kiln, fuming technology etc. are arranged respectively.Thermal process has advantages such as production efficiency is higher, unit operations is less, but its equipment investment is big, the energy consumption height.Because zinc powder dirt belongs to dangerous solid waste, before landfill, need to be cured or stabilization processes, the processing cost height, and landfill method do not recycle the useful component in the zinc powder dirt, is a kind of waste of resource.At present also do not have a kind of proper method to handle the zinc powder dirt of steel industry, pile up like a mountain to cause the zinc powder dirt of a lot of steel mills, both caused the serious environmental pollution, also make take up an area of and secondary resource to waste problem serious day by day.Therefore, effectively handling and utilize zinc powder dirt is the difficult problem that steel industry cleaner production and sustainable development must solve.
Zinc dross is the main accessory substance of negative electrode zinc metal sheet founding in the zinc hydrometallurgy factory, and zinc wherein is mainly with chloride, oxychloride, and states such as oxide and metal constitute.Electric zinc 10,000 t of every production, approximately output zinc dross 450t.Owing to contain the chlorine of 0.5-2% in the zinc dross, if direct freshening zinc, impurity chlorine will corrode positive plate, be shortened anode life and the zinc quality separated out reduces, and owing to the dechlorination difficulty, make zinc dross fail to obtain good treatment always, cause the wasting of resources.Processing to zinc dross at present has following mode: 1. most of enterprises undersell zinc dross as byproduct; 2. some enterprises produce zinc chloride and sell with salt acid treatment zinc dross; 3. pyrogenic attack zinc dross, but since the chlorine of enrichment the corrosion of equipment is not obtained promoting; 4. many scholars have carried out the research that zinc dross dechlorination, zinc dross prepare zinc oxide etc., but all be laboratory scale, are not applied to produce reality.
The present invention is in original patent of invention---a kind of method (application number 03116754.3 of producing high purity metal zinc with zinc oxide ore, publication number CN1450182A) on the basis, at zinc powder dirt and the special technology that can utilize these two kinds of trade wastes to produce metal zinc that chemical property worked out of zinc dross.Owing to contain a large amount of carbon and silica in the zinc powder dirt, and zinc dross also contains chlorine, fluorine etc., these compositions become CO when leaching
3 2-, SiO
3 2-, Cl
-And F
-Enter solution Deng anion.These anion can reduce zinc and plumbous extraction rate after the multiple cycles accumulation, therefore need to remove.The inventor is through discovering: the solubility of sodium salt and some foreign metals can reduce along with the raising of alkali concn, according to this rule, add alkali in the solution of technology of the present invention after electrolysis, sodium salt and some micro-metal impurities Crystallization Separation are come out, owing to contain alkali in these crystallizations, for the loss of avoiding alkali need be cleaned it.In cleaning process, sodium salt and foreign metal dissolving add the impurity elimination agent and make CO
3 2-, SiO
3 2-Generate precipitation etc. most of anion, foreign metal is also removed from solution together because of co-precipitation simultaneously.By above technology, solution has obtained deep purifying, when guaranteeing metal zinc quality and extraction rate, also makes the solution can recycled for multiple times, greatly reduces cost.
Summary of the invention
The objective of the invention is to disclose a kind of technology simple, with low cost with trade waste---the method that zinc powder dirt and zinc dross are produced metal zinc as raw material, product reaches GB/T6890-2000 one-level zinc powder standard.
For reaching above purpose, special feature one of the present invention is to be raw material with steel plant's zinc powder dirt and zinc hydrometallurgy factory zinc dross.The 2nd, in the remaining liquid of electrolysis, add alkali, obtain precipitation, filter, add cleaner in the filter residue.Concrete technology is as follows: at first, raw material pulverizing is arrived 0.1-1mm; Then, above-mentioned raw materials is immersed in the strong base solution, and, stir 60-100min, the zinc in zinc powder dirt and the zinc dross and plumbous dissolved at 10-100 ℃; Then, filter, filter residue washes with water, and during washery slag, the addition of water is 1-2 times (mass ratio) of filter residue, washes the back filter residue and is used for brickmaking or landfill; In the filtrate that contains zinc, lead that stays, add release agent, the addition of release agent is the 0.5-3 doubly (mass ratio) of lead content in the filtrate, stir 60min at normal temperatures after, filter, the filter residue that obtains is the leaded lead skim that reaches more than 40%, can directly sell as lead concentrate; The zinc filtrate that contains that stays is directly carried out electrolysis, deposition obtains one-level metal zinc (GB/T6890-2000) on negative electrode, the full zinc content of zinc powder reaches more than 98%, metallic zinc is characterized in that more than 96%: adopt steel plant's zinc powder dirt and zinc hydrometallurgy factory zinc dross as raw material, add alkali simultaneously in the remaining liquid of electrolytic process, obtain precipitation, filter, supernatant is got back to strong base solution, is used to leach raw material; Add precipitation wash water and cleaner in the remaining filter residue, the addition of cleaner is 0.5-3 times (mass ratio) of sodium salt content in the solution, at 10-100 ℃, stir 30-60min and filter, and filter residue landfill or brickmaking, filtrate returning is circulated in next alkali leaching flow process.
When leaching with strong alkali solution: it is in the strong base solution of 150-400g/L that the above-mentioned raw materials that crushes is immersed concentration, and its proportioning is 1 ton of raw material 3.5-10m
3Strong base solution (mass ratio).
Release agent is vulcanized sodium, sulfuration ammonia, calcium sulfide, hydrogen sulfide, magnesium sulfide sulfides and thiosulfate, can be singly with also using by a plurality of mixing of arbitrary proportion.
Cleaner is oxide and hydroxide such as magnesia, calcium oxide, barium monoxide, calcium hydroxide, magnesium hydroxide or barium hydroxide, can be singly with also using by a plurality of mixing of arbitrary proportion.
The present invention has following advantage:
1. the raw material that utilizes be should invent and the zinc powder dirt of steel plant and the zinc dross of zinc hydrometallurgy factory were, all belong to trade waste, the development and use of these unmanageable solid waste have not only been improved greatly the ecological environment of steel plant and zine-smelting plant, also reclaim and utilized useful component wherein, be to turn waste into wealth, good benefits in environment and social benefit are arranged.
2. because the present invention is dissolved in filtrate with strong base solution with the zinc in the raw material, plumbous leaching earlier, with release agent the zinc in the filtrate, lead are separated then, the filtrate that will only contain zinc at last makes the metallic zinc zinc powder with the method for electrolysis, again the remaining liquid of electrolysis is carried out deep purifying, compare with the technology of conventional process zinc powder dirt and zinc dross, this technological process is simple, easily control, equipment is simple, small investment.
3. technology of the present invention is insensitive to the variation of raw material, so long as the zinc content in zinc powder dirt and the zinc dross can utilize this PROCESS FOR TREATMENT to obtain metal zinc more than 5%, therefore the zinc waste material of the overwhelming majority can both be processed.
4. technology of the present invention is raw materials used to be discarded object, cheap, even only needs freight charges; This technology does not need high-temperature roasting; The power consumption of electrolytic metal zinc is than acid system low 20% in the aqueous slkali; Solution can be recycled in the technology, has significantly reduced the consumption of alkali.More than several make this explained hereafter metal zinc lower by 40% than traditional zinc hydrometallurgy cost, have great economic benefit.
Since in the technical process of the present invention three filter residues can both utilize, the filter residue after the leaching mixes with filter residue that causticization obtains after with alkali lye and water washing, can be used for brickmaking or landfill.Through toxicity leaching test, the filter residue avirulence can be used as Ordinary solid waste and handles.The lead skim plumbous, that zinc obtains after separating can be used as lead concentrate and sells.Both protected environment, the comprehensive utilization of having got back, economic and social benefit is all good.
Description of drawings
Fig. 1 is a process chart of the present invention
The specific embodiment
Embodiment 1
See also accompanying drawing 1.Electric furnace dust with certain steel mill is a raw material, its chemical composition such as table 1.
Table 1 zinc powder dirt chemical composition
1t zinc powder dirt is dropped into 3-3.5m
3Industrial caustic soda solution, leaching temperature are controlled at 10-95 ℃, and the concentration of industrial caustic soda solution is 200-400g/L, reaction 90min under the stirring condition at a slow speed of 120 commentaries on classics/min.Because most metals can not be dissolved in the strong base solution, so metals such as the iron in the zinc powder dirt, manganese, copper, calcium will be deposited in the form of hydroxide in the filter residue, filtrate has only zinc, lead and a spot of aluminium.Zinc and plumbous recovery rate are respectively 95% and 94% in the zinc powder.Filter, wash filter residue with water, wash water is continued to employ.In filtrate, add release agent.Release agent is a vulcanized sodium, and addition is 2.5 times (mass ratioes) of lead content in the filtrate, stirs 60min and filters, and leaded filter residue (plumbous content is 45.7%) is sold.Contain zinc filtrate (content of Zn is 24-30g/L) and directly carry out electrolysis: with Control of Voltage is 2.4-2.7V.At last, deposition obtains metal zinc on negative electrode, and full zinc is 99.12%, and metallic zinc is 97.67%, reaches one-level metal zinc standard.In the remaining liquid of electrolysis, add industrial caustic soda, obtain crystalline deposit, wash water is mixed with precipitation, the precipitation dissolving, add calcium oxide in solution, the addition of calcium oxide is 2.5 times of sodium salt in the solution, and 10-95 ℃ is stirred 60min, filter, the filtrate mixing circulation in filtrate and last step is to next leaching flow process.The loss of caustic soda is not more than 80gNaOH/kg Zn (metal) in the whole flow process.Power consumption (Kwh/kgZn) is 2.5-2.6.
Embodiment 2
Zinc dross with certain zine-smelting plant is a raw material, and its chemical composition is as follows:
Table 2 zinc dross chemical composition
In the zinc dross, zinc is based on ZnO, and zinc is also with ZnS, (CuZn) in addition
5(SO
4)
2(OH)
66HO, ZnSO
42.5H
2O, Zn
5(OH)
8Cl
22H
2The formation of compounds such as O exists, and they all are soluble in the strong base solution.Chlorine in the zinc dross exists with the NaCl form after the alkali leaching, and is very stable, can be to equipment and pole plate corrosion.Zinc dross is crushed to 0.5-1mm.Then, leach with sodium hydroxide solution: immerse 10 cubic metres of sodium hydroxide solutions by 1 ton of zinc dross and feed intake, leaching is stable to be controlled at 10-95 ℃, and the concentration of sodium hydroxide solution is 35gg/L, behind reaction 100min under the stirring condition at a slow speed of 120 commentaries on classics/min, zinc and plumbous recovery rate are 100%.Filter while hot, filter residue washes back discharging brickmaking or landfill with water, and wash water is continued to employ.Add release agent in the filtrate of containing zinc, lead that obtains after filtration, release agent is an ammonium sulfide, and the addition of release agent adds by 2 times (mass ratio) of lead content in the filtrate, through stirring reaction, filters to isolate the lead compound filter residue, is sold to plumbous smeltery.Stay and contain zinc filtrate and carry out electrolysis, voltage is 2.4-2.7V.At last, the full zinc of deposition acquisition is 99.52% on negative electrode, and metallic zinc is 98.35% one-level zinc powder.In the remaining liquid of electrolysis, add industrial caustic soda, obtain precipitation, wash water is mixed with precipitation, add barium monoxide again, barytic addition is 2 times of sodium salt in the solution, and 10-95 ℃ is stirred 60min, filter, the filtrate mixing circulation in filtrate and last step is to next leaching flow process.The loss of alkali is not more than 500kg NaOH/1tZn in the whole flow process.Power consumption (Kwh/kgZn) is 25-26.
Claims (3)
1. a method of producing metal zinc with zinc powder dirt and zinc dross at first, arrives 0.1-1mm with raw material pulverizing; Then, above-mentioned raw materials is immersed in the strong base solution, and at 10-100 ℃, stir 60-100min, then, filter, filter residue washes with water, and during washery slag, the addition of water is a 1-2 times of mass ratio of filter residue, washes the back filter residue and is used for brickmaking or landfill; Add release agent in the filtrate that stays, the addition of release agent is a 0.5-3 times of mass ratio of lead content in the filtrate, stir 60min at normal temperatures after, filter, the filter residue that obtains is the leaded lead skim that reaches more than 40%, can directly sell as lead concentrate; The zinc filtrate that contains that stays is directly carried out electrolysis, deposition obtains the one-level metal zinc on negative electrode, the full zinc content of zinc powder reaches more than 98%, metallic zinc is characterized in that more than 96%: adopt steel plant's zinc powder dirt and zinc hydrometallurgy factory zinc dross as raw material, add alkali simultaneously in the remaining liquid of electrolytic process, obtain precipitation, filter, supernatant is got back to strong base solution, is used to leach raw material; Add precipitation wash water and cleaner in the remaining filter residue, cleaner is calcium oxide or magnesia or barium monoxide or calcium hydroxide or magnesium hydroxide or barium hydroxide, or the mixture that mixes of above-mentioned several arbitrary proportion; The addition of cleaner is a 0.5-3 times of mass ratio of sodium salt content in the solution, at 10-100 ℃, stirs 30-60min and filters, and filter residue landfill or brickmaking, filtrate returning is circulated in next alkali leaching flow process.
2. a kind of method of producing metal zinc according to claim 1 with zinc powder dirt and zinc dross, it is characterized in that: described strong base solution concentration is 150-400g/L, its consumption proportion is that 1 ton of raw material needs 3.5-10 cubic meter strong base solution.
3. a kind of method of producing metal zinc according to claim 1 with zinc powder dirt and zinc dross, it is characterized in that: described release agent is single with vulcanized sodium or sulfuration ammonia or calcium sulfide or hydrogen sulfide or magnesium sulfide or thiosulfate, or presses arbitrary proportion and mix above-mentioned multiple sulfide of use or thiosulfate.
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| CN100586617C (en) * | 2007-05-29 | 2010-02-03 | 于军 | Method for recycling and preparing ultra-fine zinc dust from zinc dust containing material |
| CN101633983B (en) * | 2009-08-17 | 2010-12-01 | 蒙自矿冶有限责任公司 | Method for enhancing recovery rate of zinc fusion casting |
| CN102443708A (en) * | 2011-12-08 | 2012-05-09 | 葫芦岛锌业股份有限公司 | Device and method for extracting zinc powder from zinc casting floating slag |
| CN102978418A (en) * | 2012-12-07 | 2013-03-20 | 来宾华锡冶炼有限公司 | Processing method of casting zinc dross |
| CN103288123B (en) * | 2013-05-08 | 2015-03-11 | 洛阳市宏源化工研究所 | Method of preparing fine zinc sulfide through closed cycle |
| CN105819495A (en) * | 2016-05-30 | 2016-08-03 | 安徽省含山县锦华氧化锌厂 | Preparation method for high-activity nano-zinc oxide |
| CN108301021A (en) * | 2017-12-31 | 2018-07-20 | 昆明同越科技开发有限公司 | A method of extracting high-purity plate-like metal zinc from useless galvanized steel plain sheet surface layer |
| CN111455183B (en) * | 2020-05-14 | 2022-03-01 | 沈阳鑫迪环境技术有限公司 | Method for purifying and recovering lead and zinc by waste tire cracking carbon black |
| CN113787088A (en) * | 2021-10-29 | 2021-12-14 | 深圳市龙岗区东江工业废物处置有限公司 | CVD dust treatment method |
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