CN108588413A - A method of producing nano zine oxide using containing zinc ore crude - Google Patents
A method of producing nano zine oxide using containing zinc ore crude Download PDFInfo
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- CN108588413A CN108588413A CN201810817518.2A CN201810817518A CN108588413A CN 108588413 A CN108588413 A CN 108588413A CN 201810817518 A CN201810817518 A CN 201810817518A CN 108588413 A CN108588413 A CN 108588413A
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- zinc
- calcium
- carbonate
- nano zine
- containing zinc
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- 239000011701 zinc Substances 0.000 title claims abstract description 133
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 112
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 111
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000011575 calcium Substances 0.000 claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 230000002194 synthesizing Effects 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 11
- -1 calcium zinc Chemical compound 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 78
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 50
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 39
- 239000011787 zinc oxide Substances 0.000 claims description 39
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 35
- 230000029087 digestion Effects 0.000 claims description 35
- 239000000920 calcium hydroxide Substances 0.000 claims description 33
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 33
- 229960005069 Calcium Drugs 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- 239000000706 filtrate Substances 0.000 claims description 27
- 239000000292 calcium oxide Substances 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- NSEQHAPSDIEVCD-UHFFFAOYSA-O azanium;zinc Chemical compound [NH4+].[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-O 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 19
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 239000011667 zinc carbonate Substances 0.000 claims description 17
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 14
- LILHXQCLSOZSRO-UHFFFAOYSA-J dizinc;oxozinc;dicarbonate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[Zn+2].[Zn]=O.[Zn]=O.[Zn]=O.[O-]C([O-])=O.[O-]C([O-])=O LILHXQCLSOZSRO-UHFFFAOYSA-J 0.000 claims description 13
- 235000004416 zinc carbonate Nutrition 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N azanium;hydron;carbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- 229960003563 Calcium Carbonate Drugs 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 230000003213 activating Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L zinc;carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H Sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 235000014692 zinc oxide Nutrition 0.000 description 38
- 235000011116 calcium hydroxide Nutrition 0.000 description 23
- 239000004615 ingredient Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 7
- 229960004424 Carbon Dioxide Drugs 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- UGZADUVQMDAIAO-UHFFFAOYSA-L Zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XSMMCTCMFDWXIX-UHFFFAOYSA-N Zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 5
- 239000004110 Zinc silicate Substances 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000019352 zinc silicate Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 230000000536 complexating Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000005712 crystallization Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910007661 ZnSiO3 Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001698 pyrogenic Effects 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- HYJPZWOFVGWLCA-UHFFFAOYSA-N [Zn].[NH4+].C([O-])([O-])=O.[NH4+] Chemical compound [Zn].[NH4+].C([O-])([O-])=O.[NH4+] HYJPZWOFVGWLCA-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FWABRVJYGBOLEM-UHFFFAOYSA-N diazanium;azane;carbonate Chemical compound N.[NH4+].[NH4+].[O-]C([O-])=O FWABRVJYGBOLEM-UHFFFAOYSA-N 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010956 selective crystallization Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-N zinc;carbonic acid Chemical compound [Zn+2].OC(O)=O FMRLDPWIRHBCCC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
This disclosure relates to which a kind of utilizing the method for producing nano zine oxide containing zinc ore crude, including leach step, optional purifying step, decarbonation process, calcium zincates synthesis step, optional rinse step, calcining step, calcium zinc separating step.Disclosed method is combined wet-leaching with synthesis technology, realize the economic and environment-friendly utilization of super low-grade zinc, it is applied widely, without ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, also avoid water process pressure caused by ammonia still process, various problems such as high temperature and pressure security risk and equipment corrosion, it solves in ammonia circulation technology because steam brings the environmental issue faced due to water more than needed influences process water balance into, solve the problems, such as the technique rate of recovery and fine work grade, it pollutes small, supplies are recyclable, the calcium zincates synthesis under zinc ammonia environment is realized for the first time, and produce nano oxidized zinc product via calcium zincates.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be related to the low-grade recycling containing zinc ore crude, more particularly to one
The method that kind produces nano zine oxide using low-grade zinc oxide raw ore.
Background technology
The production of China's zinc is ranked the first in the world with consumption, and domestic zinc resource cannot meet production, need import a large amount of every year
Zinc raw material.China is one and aoxidizes the abundanter country of zinc resource, and zinc metal reserves are about 2800 in China's zinc oxide ore
Ten thousand tons, account for about 27.7% of zinc metal reserves in world's zinc oxide ore.Zinc oxide ore generally zinc grade in China's is low, average grade
Less than 5%, be still unable to the slow-witted mine of economic utilization at present, lean ore reserves account for the overwhelming majority, wherein existing stockpiling containing zinc oxide 3%~
The 5% more than one hundred million tons of mining tailing and milltailings.
Therefore, Efficient Development utilizes low-grade zinc oxide ore resource, the problem insufficient for alleviating domestic zinc raw material supply
With important strategic importance.
The main technique that low-grade zinc oxide ore utilizes includes：Pyrogenic process produces secondary zinc oxide, due to the high energy consumption of the technique
With high pollution, limited by national industrial policies.
Flotation is the main technique of current processing zinc oxide ore, but for zinc oxide floatation process, external zinc oxide ore
Sorting index is：Zinc grade 36%~40%, the rate of recovery 60%~70%, up to 78%；China's zinc oxide ore sorting index
For：Zinc grade 35%~38%, rate of recovery average out to 68%, up to 73%.Therefore recovery rate in ore-dressing is low, and concentrate grade is low etc.
Problem is common problem existing for domestic and international zinc oxide ore ore dressing, while Flotation of Zinc Oxide needs that a large amount of vulcanized sodium progress sulphur are added
Change is handled, and the zinc after vulcanization package is needed could be directly as production metallic zinc or life after pyrogenic process or pressure oxidation after-treatment
Produce the raw material of zinc oxide.
For the wet underwater welding of zinc ore, mainly there are sulfuric acid leaching, Calcium Chloride Method, ammonium chloride method etc. in the prior art.
Sulfuric acid leaching is selectively low, can largely leach the solvable silicon in ore, and the colloidal state silicon of generation is difficult to filter, and the acid-hatching of young eggs is given birth to
At a large amount of sulfate slags, great environmental protection treatment pressure is caused；Sulfuric acid leaching also can not be effectively to zinc silicate, the iron in ore
The ingredients such as sour zinc are handled.The leaching of the ingredients such as zinc silicate in raw ore, zinc ferrite can not be effectively treated in Calcium Chloride Method, and leaches
Rate is undesirable, and high temperature is needed to leach, and overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, from leaching
The process that zinc ingredient is recycled in liquid is extremely difficult, is unsuitable for commercial Application.
Therefore, existing technique is unsatisfactory to the low-grade utilization containing zinc ore crude.
Invention content
Problems to be solved by the invention
Low-grade zinc oxide ore utilizes at present technique exist energy consumption is high, recovery rate in ore-dressing is low, cause Heavy environmental pollution,
The problems such as economic value is low.The present invention is solved by the improvement to zinc oxide ore treatment process present in zinc oxide ore utilization
The above problem.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of side using the production nano zine oxide containing zinc ore crude
Method includes the following steps：
Leach step：Being mixed containing zinc ore crude and digestion agent after will be levigate, then filters, obtains leachate, wherein
The digestion agent be ammonia and ammonium hydrogen carbonate mixed aqueous solution or ammonia and the mixed aqueous solution or ammonia of ammonium carbonate, ammonium hydrogen carbonate and
The mixed aqueous solution of ammonium carbonate；
Optionally, the leachate obtained in the leach step is purified；
Decarbonation process：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains first
Solid and the first filtrate；
Calcium zincates synthesis step：Activating agent is added to first filtrate, adds calcium hydroxide and/or calcium oxide, stirs
It mixes, then filters, obtain the second solid and the second filtrate；
Optionally, second solid is rinsed with water；
Calcining step：Second solid is taken to be calcined, calcination temperature is 150~1050 DEG C, preferably 150~350 DEG C；
Calcium zinc separating step：The calcined product that the calcining step obtains is mixed with water, is stirred, filtering obtains third
The third solid is dried, obtains nano oxidized zinc product by solid and third filtrate.
It is described in the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude
The mass concentration of total ammonia in digestion agent is 5%~15%, and the molar concentration of effective carbonate in the digestion agent is：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein,
CDigestion agent carbonateFor the molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
VDigestion agentFor the volume of the digestion agent,
The value range of a is 100%~600%, preferably 150%~250%.
In the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude, in institute
It states in the leachate that leach step obtains, the concentration (in terms of quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L.
In the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude, in institute
The amount for stating the substance of the calcium oxide and/or calcium hydroxide that are added in decarbonation process is the object of effective carbonate in the leachate
The 100% to 130% of the amount of matter, preferably 100% to 110%.
In the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude, in institute
It states in calcium zincates synthesis step, amount and the first filter of the substance of calcium hydroxide and/or calcium oxide is added into first filtrate
The ratio between amount of substance of zinc ammonium complex ion is 1~1.2 in liquid:2, preferably 1~1.1:2.
In the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude, to institute
State second filtrate that calcium zincates synthesis step obtains and be passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as
Digestion agent is recycled for the extraction containing zinc ore crude.
It is described in the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude
The reaction temperature of calcium zincates synthesis step is 15~90 DEG C, preferably 15~25 DEG C.
It is described in the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude
The time that is stirred to react of calcium zincates synthesis step is 15~30 minutes.
In the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude, in institute
It states in calcium zinc separating step, is passed through carbon dioxide to the third filtrate, obtains precipitation of calcium carbonate.
It is described in the utilization that disclosure further embodiment provides produces the method for nano zine oxide containing zinc ore crude
Activating agent is one or more in calgon, neopelex.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects：
1) wet-leaching is combined with synthesis technology, realizes the economic and environment-friendly utilization of super low-grade zinc.
2) disclosed method is applied widely, and ammonia-ammonium bicarbonate Leaching Systems can be effectively former containing zinc to diversified forms
Mine is extracted and is utilized.
3) break traditional ammonia-ammonium carbonate method zinc complexing extracting technology by heating evaporation ammonia destroy complexing environment realize zinc from
Calcium oxide or hydroxide are added creatively into ammonium bicarbonate-zinc ammonia complex system by the orthodox practice of sub- Crystallization Separation, the application
Calcium makes the balance of zinc ammonium complex ion-zinc ion-calcium zincates move, by flat under the premise of not destroying solution ammonia environment
The shifting principle that weighs realizes the selective crystallization separation of Zn-ef ficiency, and avoiding existing heating ammonia still process method from destroying ammonia environment causes impurity a large amount of
The phenomenon that co-precipitation.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, greatly reduces the energy consumption of technique, it is thus also avoided that ammonia still process
Various problems such as caused water process pressure, high temperature and pressure security risk and equipment corrosion.
4) leaching and separation that zinc is realized by the cycle of carbonate solve in ammonia circulation technology because steam brings water more than needed into
Measure the environmental issue for influencing process water balance and facing.
5) relative to zinc oxide floatation process, disclosed method solves the problems, such as the technique rate of recovery and fine work grade, institute
The raw material that the product obtained directly as product, can also can be used as other industrial process uses.
6) disclosed method pollution is small, and supplies are recyclable, and it is former to solve existing zinc oxide treatment process auxiliary
The problem of environmental pollution that material strip comes.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, and produces nano zine oxide via calcium zincates
Product；The reaction selectivity that calcium zincates are synthesized from zinc ammonium complex ion is high, simple and quick.
Specific implementation mode
It will be detailed below various exemplary embodiments, feature and the aspect of the disclosure.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Any embodiment here as illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, in order to which the disclosure is better described, numerous details is given in specific implementation mode below.
In some instances, method well known to those skilled in the art, means, reagent and equipment are not described in detail, but ability
Field technique personnel can realize the technical solution of the disclosure according to the general knowledge of this field.
The scope of application of disclosed method is not particularly limited, and is widely portable to the various utilizations containing zinc ore crude.
When using low-grade zinc oxide raw ore as raw materials for production, the advantages of method disclosed herein, is particularly pertinent.For example, low-grade former containing zinc
Mine can be zinc content contains zinc ore crude 3%~15%；Particularly, before the disclosure, zinc content contains 3%~6%
Zinc ore crude (lean ore, milltailings) is largely stored up, and existing various techniques are to can not make the utilization of existing economic value in fact
At prodigious processing pressure, and disclosed method is not only technically realized to such low-grade containing the effective of zinc ore crude
It utilizes, and simple process is easy, it is of low cost, there is very high economic value.
In the disclosure, the existence form containing zinc ingredient in zinc ore crude is not particularly limited, such as zinc ingredient can be with packet
The one or more forms for including but being not limited to zinc oxide, zinc carbonate, zinc silicate etc. exist.
Explanation of nouns
Herein, unless otherwise indicated, " ammine carbonate zinc " is the compound that zinc ammonium complex ion is formed with carbonate
General name, including [Zn (NH3)4]CO3(four ammino zinc of carbonic acid), [Zn (NH3)3]CO3(three ammino zinc of carbonic acid), [Zn (NH3)2]CO3
(two ammino zinc of carbonic acid), [Zn (NH3)]CO3(one ammino zinc of carbonic acid) etc..
Herein, unless otherwise indicated, " zinc ammonium complex ion " is the general name of ammino zinc complex ions at different levels, including [Zn
(NH3)4]2+(four ammino zinc ions), [Zn (NH3)3]2+(three ammino zinc ions), [Zn (NH3)2]2+(two ammino zinc ions), [Zn
(NH3)]2+(an ammino zinc ion) etc..
Herein, unless otherwise indicated, in solution (including but not limited to the various liquid such as digestion agent, leachate)
" effective carbonate " refers to the summation of carbonate and bicarbonate radical in the solution.
" optional " or " optionally " indicates that the then described step can carry out, or can be without, and the table
State the situation carried out including the then described step and the then described step without situation.
Chemical equation
1. extraction
A. zinc oxide extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
ZnO+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O (integer that i is 1 to 4)
Ammonia is with ammonium carbonate as digestion agent
ZnO+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O (integer that i is 2 to 4)
B. zinc hydroxide extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
Zn(OH)2+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 1 to 4)
Ammonia is with ammonium carbonate as digestion agent
Zn(OH)2+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 2 to 4)
C. zinc carbonate (smithsonite) extracts
ZnCO3+iNH3=[Zn (NH3)i]CO3(integer that i is 1 to 4)
D. zinc silicate extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
ZnSiO3+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 1 to 4)
Ammonia is with ammonium carbonate as digestion agent
ZnSiO3+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 2 to 4)
2. decarburization
Lime is reacted with water
CaO+H2O=Ca (OH)2
Precipitation
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
[Zn(NH3)i]CO3+Ca(OH)2=[Zn (NH3)i](OH)2+CaCO3↓
(integer that i is 1 to 4)
The side reaction that may occur：
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
3. calcium zincates synthesize
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O=Ca (OH)2·2Zn(OH)2·2H2O+2iNH3
(integer that i is 1 to 4)
4. calcining
Ca(OH)2·2Zn(OH)2·2H2O=Ca (OH)2+2ZnO+4H2O
Or
Ca(OH)2·2Zn(OH)2·2H2O=CaO+2ZnO+5H2O
Specific process step
Step 1 extracts
Low-grade be mixed in a certain ratio with prepared digestion agent containing zinc ore crude after will be levigate is stirred leaching.Leaching
Proposing agent can be selected from：The mixed aqueous solution of ammonia and ammonium hydrogen carbonate；The mixed aqueous solution of ammonia and ammonium carbonate；Ammonia, ammonium hydrogen carbonate and carbon
The mixed aqueous solution of sour ammonium.
Total ammonia density and effective carbonate concentration in digestion agent are not particularly limited, and those skilled in the art can be according to original
The factors such as mine ingredient, grade, are selected in conjunction with actual needs.
In the preferred scheme, the mass concentration of total ammonia is 5%~15%, more preferable 6%~8% in digestion agent, preferably
Concentration range can reach sufficient extracting effect, and avoid excessive ammonia cause waste and environmental issue.
In the preferred scheme, the amount of effective carbonate is to subtract original in complexing zinc theory carbonate consumption in digestion agent
Increase by 0~500% on the basis of the difference obtained by carbonate amount that zinc carbonate is brought into material, effective carbonate in more preferable digestion agent
Amount increase on the basis of zinc theory carbonate consumption is complexed and subtracts the difference obtained by the carbonate amount that zinc carbonate in raw material is brought into
Add 50%-150%.It refers to that the Zn-ef ficiency in raw ore is fully converted to ammine carbonate zinc institute that zinc theory carbonate consumption, which is complexed,
The amount of the carbonate of consumption.Therefore, the molar concentration of effective carbonate may be calculated as in digestion agent：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein, CDigestion agent carbonateFor the molar concentration of effective carbonate in digestion agent, nThe total zinc of raw oreFor containing the Zn-ef ficiency in zinc ore crude
Substance amount, nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude, VDigestion agentFor digestion agent volume, a is coefficient, a's
Value is 100%~600%, preferably 150%~250%.The mass concentration of carbonate can be changed according to molar concentration in digestion agent
It calculates.
It is complete that the preferred effective carbonate concentration of digestion agent can be such that the zinc in raw ore leaches, and carbonate can be realized in work
Cycle in skill, and it is avoided that excessive carbonate causes stress subsequent technique processing.
The weight ratio of digestion agent and the powder containing zinc ore crude is not particularly limited, as long as zinc ingredient can be leached.It is preferred that
The weight ratio of digestion agent and the powder containing zinc ore crude is 3:1 to 5:1, satisfied extracting effect can be not only obtained, but also avoid the wave of digestion agent
Take.
The temperature of extraction is not particularly limited, as long as the zinc ingredient in raw ore is made to be leached.It is preferred that at normal temperatures into
Row extraction, such as extracted at 15~30 DEG C；Also it (such as 30~55 DEG C) can be extracted at slightly higher temperature.It also can root
Suitable temperature is selected according to physical condition.
It is stirred after oxidation zinc ore crude is mixed with digestion agent, mixing time is not particularly limited, as long as making in raw ore
Zinc ingredient be leached, preferably mixing time be 1~4 hour, more preferable 1~2 hour.
In leaching process, the Zn-ef ficiency in raw ore be converted into zinc ammonium complex ion (the zinc ammino formed in leaching process from
Son is mainly zinc ammonium complex ions at different levels), into liquid phase.It is filtered, obtains after filtering containing zinc ammonium complex ion after extraction
Leachate.Leachate can be used for subsequent decarbonizing process.Zinc ammonium complex ion concentration in leachate is not particularly limited, but preferably
Zinc ammonium complex ion concentration (in terms of quality of Zn-ef ficiency) in leachate is 10~25g/L, and the treatment effeciency of technique can be made optimal,
Good yield and purity are obtained in subsequent calcium zincates synthesis step, overall economic efficiency is best.
Step 2 purifies
Step 2 be optional step, it is necessary to when selection carry out step 2.Leachate is purified by known method,
Remove the impurity elements such as iron, manganese, lead, copper.A kind of illustrative purification method is then addition zinc powder is filtered into line replacement, to
Heavy metal contaminants are removed, but other various well known purification methods can also be used.Purifying step helps to improve finished product
Purity.
Step 3 decarburization
In decarbonation process, calcium hydroxide and/or calcium oxide are added into the leachate containing zinc ammonium complex ion, will leach
Carbonate/bicarbonate in liquid switchs to calcium carbonate.If zinc ammonium complex ion excessive concentration in leachate, it is likely that send out simultaneously
The balanced sequence of zinc ammonium complex ion-zinc ion-zinc hydroxide in raw leachate, a little zinc ingredient may be with hydroxide
The form of zinc is co-precipitated with calcium carbonate.
In decarbonation process, effective carbonate in the substantially matching leachate of additive amount of calcium hydroxide and/or calcium oxide
Content, for example, the amount of the substance of calcium hydroxide and/or calcium oxide that decarbonation process is added is the object of effective carbonate in leachate
The 100% to 130% of the amount of matter, more preferable 100% to 110%.Calcium hydroxide and/or calcium oxide are appropriately added, is contributed to
Control process costs, it helps improve the purity and quality of finished product zinc product.
In decarbonation process, calcium hydroxide and/or calcium oxide are added into leachate, stirring is reacted, and solid is generated
Precipitation.The temperature of reaction is not particularly limited, and is particularly preferably reacted at normal temperatures (such as 15~25 DEG C), on the one hand saves
The energy, environmental pollution caused by the other hand also reducing ammonia volatilization.Mixing time is not particularly limited, and is as long as obtaining precipitation
Can, preferably stir 1~2 hour.
It is filtered after stirring, obtains the first solid and the first filtrate.The main component of first solid is calcium carbonate, if
The concentration of zinc ammonium complex ion is higher in leachate, then some hydroxides being co-precipitated with calcium carbonate are also likely to be present in the first solid
Zinc.First filtrate continues on for subsequent calcium zincates synthesis.Calcium carbonate in first solid can then be calcined to calcium oxide and two
Carbonoxide, realization recycle.
Step 4 calcium zincates synthesize
Activating agent, calcium hydroxide and/or calcium oxide is added in the first filtrate obtained to step 3, and stirring is reacted.This step
The amount and the ratio between amount of substance of zinc ammonium complex ion in the first filtrate of the substance of the calcium hydroxide and/or calcium oxide that are added in rapid are excellent
Select 1~1.2:2, more preferable 1~1.1:2.The temperature of reaction is not particularly limited, and may, for example, be 15~90 DEG C, but especially excellent
Choosing is reacted (such as 15~25 DEG C) at normal temperatures, on the one hand energy saving, ring caused by the other hand also reducing ammonia volatilization
Border is polluted, while low temperature is more advantageous to control crystallization particle diameter.
Mixing time is not particularly limited, as long as being precipitated, but in order to control crystallization particle diameter, is preferably stirred to react
It can be filtered after 15~30 minutes, without prolonged reaction and ageing process.Be obtained by filtration with calcium zincates be mainly at
The second solid divided and the second filtrate.It can be passed through carbon dioxide to the second filtrate, then recycled for the extraction containing zinc ore crude.
The preferred calgon of activating agent or neopelex being added in this step, dosage are preferably estimated
The 0.01~0.05% of finished product quality.
Step 5 calcium zincates rinse
Step 5 be optional step, it is necessary to when selection carry out step 5.In steps of 5, for based on calcium zincates
The second solid for wanting ingredient, adds water to be rinsed, and liquid-solid ratio is 5~10:1, rinsing times are 1-2 times.
Step 6 is calcined
In this step, it takes the second solid to be calcined, calcium zincates is made to decompose.Calcination temperature is at 150~1050 DEG C, preferably
150~350 DEG C.It is mixture to calcine obtained product, if calcination temperature at 150~350 DEG C, calcined product main component
For zinc oxide and calcium hydroxide；If using higher calcination temperature, calcined product contain zinc oxide, calcium hydroxide and/or
Calcium oxide.
Step 7 calcium zinc detaches
It is insoluble in water in view of zinc oxide, and calcium hydroxide (or calcium oxide) is water-soluble or is dissolved in water after being reacted with water, therefore
Water solubility using zinc oxide and calcium hydroxide (or calcium oxide) is poor, realizes zinc oxide and calcium hydroxide (or calcium oxide)
Separation.
In this step, the calcined product that step 6 obtains is mixed with water, is stirred, filtering obtains third solid and third
Filtrate.The main component of third solid is zinc oxide, and the solute in third filtrate is mainly calcium hydroxide.Third solid is done
It is dry, finished product nano zine oxide is obtained, the average grain diameter of product is 10~100nm.And for third filtrate, it can be passed through to it
Carbon dioxide obtains precipitation of calcium carbonate, and also recyclable third filtrate supplies other purposes.
The embodiment of the disclosure is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the disclosure, and is not construed as the restriction to the scope of the present disclosure.It is not specified in embodiment
Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer,
Being can be with conventional products that are commercially available.
Embodiment 1
Yunnan somewhere zinc ore, Zn content 5.6%, raw ore oxygenation efficiency 96.3%, the zinc ingredient in the mine is based on zinc carbonate
Want existence form.
It takes 300 grams to contain zinc ore crude, is put into 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate matter
Amount concentration 3%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, filtered liquid
Contain zinc (gauge is worked as with zinc oxide) 1.632% in body, carbonate mass concentration 4.23% in liquid, increased portion is divided into raw ore
Zinc carbonate is brought into.According to inspection data, solvable zinc recovery is 90.79% in leaching process raw ore, and total zinc recovery is
87.43%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
600 milliliters of purified leachates are taken, 14.55 grams of calcium oxide are added, for precipitating carbonate, after reacting 1 hour
It is filtered.
Take 500 milliliters of filtered liquid, 3 milligrams of neopelexes, 2.45 grams of calcium hydroxides be added, stir into
Row reaction, reaction are filtered after 1 hour, are obtained after filtering with calcium zincates solid as main component.
Calcium zincates solid is dried 2 hours at 105 DEG C, then is calcined 2 hours through 300 DEG C, calcium zincates are decomposed into oxygen
Change zinc and calcium hydroxide.
The water of 300 times of quality is added to zinc oxide and calcium hydroxide, stirs 1 hour, is then filtered, will be obtained by filtration
Nano zine oxide dry 2 hours at 105 DEG C, analysis of testing, the content of zinc oxide is 99.56% in product, is aoxidized
The average grain diameter of zinc is 49.3nm.
Embodiment 2
Chongqing somewhere zinc ore, Zn content 4.7%, raw ore oxygenation efficiency 95.52%, the zinc ingredient in the mine is based on zinc silicate
Want existence form.
300 grams of oxidation zinc ore crudes are taken, 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate are put into
Mass concentration 3%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, liquid after filtering
Zinc oxide 1.367% is pressed in body, carbonate mass concentration 3.54% in liquid, increased portion is divided into the zinc carbonate in raw ore and brings into.
According to inspection data, solvable zinc recovery is 91.35% in leaching process raw ore, and total zinc recovery is 87.26%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
600 milliliters of purified leachates are taken, 12.18 grams of calcium oxide are added, for precipitating carbonate, after reacting 1 hour
It is filtered.
500 milliliters of filtered liquid is taken, 3 milligrams of neopelexes, 2 grams of calcium hydroxides are added, stirring carries out
Reaction, reaction are filtered after 1 hour, are obtained after filtering with calcium zincates solid as main component.
Calcium zincates solid is dried 2 hours at 105 DEG C, then is calcined 2 hours through 300 DEG C, calcium zincates are decomposed into oxygen
Change zinc and calcium hydroxide.
The water of 300 times of quality is added to zinc oxide and calcium hydroxide, stirs 1 hour, is then filtered, will be obtained by filtration
Nano zine oxide dry analysis of testing in 2 hours at 105 DEG C, the content of zinc oxide is 99.45% in product, zinc oxide
Average grain diameter be 57.2nm.
The presently disclosed embodiments is described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.The selection of term used herein, purport
In principle, the practical application or to the technological improvement in market for best explaining each embodiment, or make the art its
Its those of ordinary skill can understand each embodiment disclosed herein.
Claims (10)
1. a kind of utilizing the method for producing nano zine oxide containing zinc ore crude, which is characterized in that described to be received using the production containing zinc ore crude
The method of rice zinc oxide includes the following steps：
Leach step：Being mixed containing zinc ore crude and digestion agent after will be levigate, then filters, obtains leachate, wherein is described
Digestion agent is ammonia and the mixed aqueous solution or ammonia of ammonium hydrogen carbonate and mixed aqueous solution or ammonia, the ammonium hydrogen carbonate and carbonic acid of ammonium carbonate
The mixed aqueous solution of ammonium；
Optionally, the leachate obtained in the leach step is purified；
Decarbonation process：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains the first solid
With the first filtrate；
Calcium zincates synthesis step：Activating agent is added to first filtrate, adds calcium hydroxide and/or calcium oxide, stirs, so
After filter, obtain the second solid and the second filtrate；
Optionally, second solid is rinsed with water；
Calcining step：Second solid is taken to be calcined, calcination temperature is 150~1050 DEG C, preferably 150~350 DEG C；
Calcium zinc separating step：The calcined product that the calcining step obtains is mixed with water, is stirred, filtering obtains third solid
With third filtrate, the third solid is dried, nano oxidized zinc product is obtained.
2. according to claim 1 utilize the method for producing nano zine oxide containing zinc ore crude, which is characterized in that
The mass concentration of total ammonia in the digestion agent is 5%~15%, effective carbonate in the digestion agent it is mole dense
Degree is：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein,
CDigestion agent carbonateFor the molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
VDigestion agentFor the volume of the digestion agent,
The value range of a is 100%~600%, preferably 150%~250%.
3. according to claim 1 or 2 utilize the method for producing nano zine oxide containing zinc ore crude, which is characterized in that in institute
It states in the leachate that leach step obtains, the concentration (in terms of quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L.
4. according to any one of claims 1 to 3 using the method for producing nano zine oxide containing zinc ore crude, feature exists
In the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the decarbonation process is effective carbon in the leachate
The 100% to 130% of the amount of the substance of acid group, preferably 100% to 110%.
5. according to any one of claims 1 to 4 using the method for producing nano zine oxide containing zinc ore crude, feature exists
In, in the calcium zincates synthesis step, be added into first filtrate amount of the substance of calcium hydroxide and/or calcium oxide with
The ratio between amount of substance of zinc ammonium complex ion is 1~1.2 in first filtrate:2, preferably 1~1.1:2.
6. according to any one of claims 1 to 5 using the method for producing nano zine oxide containing zinc ore crude, feature exists
In second filtrate obtained to the calcium zincates synthesis step is passed through carbon dioxide, will be passed through the second of carbon dioxide
Filtrate recycles as digestion agent for the extraction containing zinc ore crude.
7. according to any one of claims 1 to 6 using the method for producing nano zine oxide containing zinc ore crude, feature exists
In the reaction temperature of the calcium zincates synthesis step is 15~90 DEG C, preferably 15~25 DEG C.
8. according to any one of claims 1 to 7 using the method for producing nano zine oxide containing zinc ore crude, feature exists
In the time that is stirred to react of the calcium zincates synthesis step is 15~30 minutes.
9. utilizing the method for producing nano zine oxide containing zinc ore crude according to claim 1 to 8 any one of them, feature exists
In in the calcium zinc separating step, being passed through carbon dioxide to the third filtrate, obtain precipitation of calcium carbonate.
10. utilizing the method for producing nano zine oxide containing zinc ore crude according to claim 1 to 9 any one of them, feature exists
In the activating agent is one or more in calgon, neopelex.
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|---|---|---|---|
| CN201810817518.2A CN108588413A (en) | 2018-07-24 | 2018-07-24 | A method of producing nano zine oxide using containing zinc ore crude |
| PCT/CN2019/084003 WO2020019777A1 (en) | 2018-07-24 | 2019-04-24 | Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate |
| CN201980001299.3A CN110896643B (en) | 2018-07-24 | 2019-04-24 | Method for producing zinc-containing compound or zinc oxide from zinc-containing raw ore through intermediate step of calcium zincate synthesis |
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| CN201810817518.2A CN108588413A (en) | 2018-07-24 | 2018-07-24 | A method of producing nano zine oxide using containing zinc ore crude |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019777A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate |
| WO2020019834A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Mineral processing method for low-grade zinc-containing raw ore |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019777A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate |
| WO2020019834A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Mineral processing method for low-grade zinc-containing raw ore |
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