CN108866332A - A kind of low-grade beneficiation method containing zinc ore crude - Google Patents
A kind of low-grade beneficiation method containing zinc ore crude Download PDFInfo
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- CN108866332A CN108866332A CN201810817494.0A CN201810817494A CN108866332A CN 108866332 A CN108866332 A CN 108866332A CN 201810817494 A CN201810817494 A CN 201810817494A CN 108866332 A CN108866332 A CN 108866332A
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- Prior art keywords
- zinc
- carbonate
- calcium
- amount
- leachate
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- 239000011701 zinc Substances 0.000 title claims abstract description 177
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 150
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 147
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 68
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011575 calcium Substances 0.000 claims abstract description 41
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 38
- 239000011787 zinc oxide Substances 0.000 claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 230000002194 synthesizing Effects 0.000 claims abstract description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 96
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 75
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 60
- 239000000920 calcium hydroxide Substances 0.000 claims description 56
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 56
- 239000000292 calcium oxide Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 48
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 46
- 239000000126 substance Substances 0.000 claims description 40
- 239000000706 filtrate Substances 0.000 claims description 39
- 229960005069 Calcium Drugs 0.000 claims description 36
- 230000029087 digestion Effects 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- NSEQHAPSDIEVCD-UHFFFAOYSA-O azanium;zinc Chemical compound [NH4+].[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-O 0.000 claims description 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 23
- 229960003563 Calcium Carbonate Drugs 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 239000011667 zinc carbonate Substances 0.000 claims description 17
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 238000002386 leaching Methods 0.000 claims description 15
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002203 pretreatment Methods 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
- 238000003756 stirring Methods 0.000 claims description 13
- 235000004416 zinc carbonate Nutrition 0.000 claims description 13
- FMRLDPWIRHBCCC-UHFFFAOYSA-L zinc;carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 40
- 235000014692 zinc oxide Nutrition 0.000 description 31
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- UGZADUVQMDAIAO-UHFFFAOYSA-L Zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 18
- 229940007718 zinc hydroxide Drugs 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- 230000001376 precipitating Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000536 complexating Effects 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000000243 solution 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
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 235000019352 zinc silicate Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 229960004424 Carbon Dioxide Drugs 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 229910007661 ZnSiO3 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 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
- VMLAJPONBZSGBD-UHFFFAOYSA-L calcium;hydrogen carbonate;hydroxide Chemical compound [OH-].[Ca+2].OC([O-])=O VMLAJPONBZSGBD-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon 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
- 238000000151 deposition Methods 0.000 description 2
- YVEWQBBNXXNHKX-UHFFFAOYSA-J dizinc;zinc;dicarbonate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn].[Zn].[Zn].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O YVEWQBBNXXNHKX-UHFFFAOYSA-J 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000002075 main ingredient 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
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001698 pyrogenic Effects 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 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
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 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
- 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 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
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 leachate Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation 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
- 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
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
-
- 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 a kind of low-grade beneficiation method containing zinc ore crude, including leach step, settling step, calcium zincates synthesis step, drying steps.Disclosed method realizes the economic and environment-friendly utilization of ultra-low oxidized zinc ore, it is applied widely, it is not necessarily to ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, it is thus also avoided that various problems such as water process pressure caused by ammonia still process, high temperature and pressure security risk and equipment corrosion；Disclosed method solves the problems, such as the technique rate of recovery and fine work grade, and raw material needs secondary treatment technical process after solving vulcanizing treatment；Disclosed method pollution is small, and supplies are recyclable, solves the problems, such as existing zinc oxide treatment process auxiliary material bring environmental pollution；The disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time.
Description
Technical field
The invention belongs to the complex art fields of inorganic chemical industry and ore-dressing technique, are related to the low-grade recycling containing zinc ore crude
It utilizes, in particular to a kind of low-grade beneficiation method containing zinc ore crude.
Background technique
The production of China's zinc is ranked the first in the world with consumption, and domestic zinc resource is not able to satisfy production, needs import a large amount of every year
Zinc raw material.China is an oxidation zinc resource country more abundant, 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, for alleviating the insufficient problem of 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 ore floatation process, external zinc oxide
Mine sorting index is：Zinc grade 36%~40%, the rate of recovery 60%~70%, up to 78%；China's zinc oxide ore sorts finger
It is designated as：Zinc grade 35%~38%, rate of recovery average out to 68%, up to 73%.Flotation of Zinc Oxide needs to be added a large amount of simultaneously
Vulcanized sodium carries out vulcanizing treatment, and zinc sulphide needs that after pyrogenic attack, directly as production metallic zinc or zinc oxide could be produced
Raw material, energy consumption are high and seriously polluted.
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 raw
At a large amount of sulfate slags, great environmental protection treatment pressure is caused；Sulfuric acid leaching also can not in ore zinc silicate, zinc ferrite at
Divide and is 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 leaching rate is paid no attention to
Think, need high temperature to leach, overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, returned from leachate
The process for receiving zinc ingredient is extremely difficult, is unsuitable for industrial application.
Therefore, existing technique to it is low-grade containing zinc ore crude using unsatisfactory.
Summary of the invention
Problems to be solved by the invention
The technique that low-grade zinc utilizes at present is high in the presence of energy consumption, recovery rate in ore-dressing is low, causes Heavy environmental pollution, economy
It is worth the problems such as low.The present invention solves above-mentioned present in low-grade zinc utilization ask by the improvement to zinc ore treatment process
Topic.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of low-grade beneficiation method containing zinc ore crude, including
Following steps：
Leach step：Being mixed after will be levigate containing zinc ore crude and digestion agent, 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；
Settling step：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：Calcium hydroxide and/or calcium oxide are added into first filtrate, stirring is reacted,
The second solid and the second filtrate is obtained by filtration；
Drying steps：Take second solid to be dried, or by some or all of described first solid with it is described
Some or all of second solid mix then drying, obtains finished product.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the precipitating
The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in rapid is the amount of the substance of effective carbonate in the leachate
100% to 130%, preferably 100% to 110%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, the settling step
It is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added into the leachate that the leach step obtains, and are stirred
It mixes, pre-treated solid and intermediate filtrate is obtained by filtration,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, stirring,
Filtering obtains heavy zinc solid and the first filtrate；
In the drying steps, the pre-treated solid, the heavy zinc solid is taken to mix with second solid, then
It is dried；Or the heavy zinc solid is taken to mix with second solid, then it is dried.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, in the pretreatment
The amount of the calcium hydroxide and/or calcium oxide that add in step is：
nPretreatment=(nLeachate carbonate-nZinc ammonium complex ion)×b
Wherein,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the leachate,
The value of b is 0<B≤110%, the preferably value of b are 90%≤b≤110%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the heavy zinc
The calcium hydroxide of addition and/or the amount of calcium oxide are in rapid：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein,
nHeavy zincTo sink the amount of the substance of calcium hydroxide and/or calcium oxide added in zinc step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the pre-treatment step,
The value of c is 100%≤c≤130%, and preferably the value of c is 100%≤c≤110%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, in the digestion agent
Total ammonia mass concentration be 5%~15%, preferably 6%~8%,
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%, and preferably the value range of a is 150%~250%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, in the calcium zincates
The object of zinc ammonium complex ion in the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in synthesis step and first filtrate
The ratio between amount of matter is 1~1.2:2, preferably 1~1.1:2.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, to the calcium zincates
Second filtrate that synthesis step obtains is passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as digestion agent,
Circulation is for the extraction containing zinc ore crude.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides：
In the drying steps, not higher than 125 DEG C at a temperature of be dried, the finished product be contain carbonic acid
The mixture of calcium, zinc hydroxide and calcium zincates；
Alternatively, in the drying steps, 150~350 DEG C at a temperature of be dried, the finished product is to contain carbon
The mixture of sour calcium, zinc oxide and calcium hydroxide.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the precipitating
In rapid, reacted in 15~25 DEG C of at a temperature of stirring.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects：
1) by wet-leaching in conjunction with ore-dressing technique, the economic and environment-friendly utilization of super low-grade zinc is realized.
2) disclosed method is applied widely, and ammonia-ammonium bicarbonate Leaching Systems can be effectively to the former containing zinc of 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 moves zinc ammonium complex ion-zinc ion-zinc hydroxide balance, passes through under the premise of not destroying solution ammonia environment
Balance moving principle realizes the selective crystallization separation of Zn-ef ficiency, and avoiding existing heating ammonia still process method from destroying ammonia environment causes impurity big
The phenomenon that amount 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 steams
Various problems such as water process pressure caused by ammonia, high temperature and pressure security risk and equipment corrosion.
4) disclosed method solves the problems, such as the technique rate of recovery and fine work grade, and raw material needs two after solving vulcanizing treatment
The deficiency of secondary treatment process process.
5) disclosed method pollution is small, and supplies are recyclable, and it is former to solve existing zinc oxide treatment process auxiliary
The problem of expecting bring environmental pollution.
6) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, from the reaction of zinc ammonium complex ion synthesis calcium zincates
Selectivity is high, simple and quick.
Specific embodiment
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 ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, giving numerous details in specific embodiment below in order to which the disclosure is better described.
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.?
Using it is low-grade containing zinc ore crude as raw materials for production when, the advantages of method disclosed herein, is particularly pertinent.For example, low-grade contain zinc ore crude
Zinc content be can be 3%~15% containing zinc ore crude；Particularly, before the disclosure, zinc content is 3%~6% containing zinc
Raw ore (lean ore, milltailings) is largely stored up, and existing various techniques are to can not cause the utilization of existing economic value in fact
Very big processing pressure, and disclosed method is not only technically realized to such low-grade effective benefit containing zinc ore crude
With, and simple process is easy, and it is low in 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 zinc ammonium complex ion and the compound that carbonate is formed
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, solution (the including but not limited to various liquid such as digestion agent, leachate, intermediate filtrate
Body) in " effective carbonate " refer to the summation of carbonate and bicarbonate radical in the solution.
Chemical equation
1. extraction
A. zinc oxide extracts
Ammonia and ammonium hydrogen carbonate are as digestion agent
ZnO+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O (integer that i is 1 to 4)
Ammonia and ammonium carbonate are 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 and ammonium hydrogen carbonate are as digestion agent
Zn(OH)2+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 1 to 4)
Ammonia and ammonium carbonate are 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 and ammonium hydrogen carbonate are as digestion agent
ZnSiO3+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 1 to 4)
Ammonia and ammonium carbonate are as digestion agent
ZnSiO3+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 1 to 4)
2. precipitating
Lime is reacted with water
CaO+H2O=Ca (OH)2
Precipitating
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
[Zn(NH3)i]CO3+Ca(OH)2=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
[Zn(NH3)i]CO3+Ca(OH)2=[Zn (NH3)i](OH)2+CaCO3↓
(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(i be 1 to 4 it is whole
Number)
4. dry
Zn(OH)2=ZnO+H2O
Ca(OH)2·2Zn(OH)2·2H2O=Ca (OH)2+2ZnO+4H2O
Specific process step
Step 1 extraction
Low-grade be mixed in a certain ratio containing zinc ore crude and prepared digestion agent 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.It is preferred that
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 difference obtained by the carbonate amount that zinc carbonate is brought into material, effective carbonate in more preferable digestion agent
Amount be complexed zinc theory carbonate consumption subtract difference obtained by the carbonate amount that zinc carbonate in raw material is brought on the basis of increase
Add 50%-150%.Complexing zinc theory carbonate consumption, which refers to, is fully converted to ammine carbonate zinc institute for the Zn-ef ficiency in raw ore
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 carbonate effective 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.
The preferred effective carbonate concentration of digestion agent can be such that the zinc in raw ore leaches completely, and carbonate can be realized in work
Circulation 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 being leached the zinc ingredient in raw ore.It is preferred that at normal temperature into
Row extraction, such as extracted at 15~30 DEG C；It (such as 30~55 DEG C) can also be extracted at a temperature of slightly higher.It can also root
Suitable temperature is selected according to physical condition.
It will contain after zinc ore crude is mixed with digestion agent and be stirred, mixing time is not particularly limited, as long as making in raw ore
Zinc ingredient is leached, and preferably mixing time is 1~4 hour, more preferable 1~2 hour.
In leaching process, the Zn-ef ficiency in raw ore is converted into zinc ammonium complex ions at different levels, into liquid phase.It is carried out after extraction
Filtering, obtains the leachate containing zinc ammonium complex ion, leachate can be used for subsequent precipitation process after filtering.Zinc in leachate
Ammonium complex ion concentration is not particularly limited, but the zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) preferably in leachate exists
10g/L or more, more preferable 10~50g/L can make disclosed method overall economic efficiency best.It optionally, if it is necessary, can
Leachate is purified with existing conventional method.
Step 2 precipitating
In settling step, 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, while zinc ammonium complex ion-zinc ion-zinc hydroxide balance in leachate
It moves, part zinc ammonium complex ion is decomposed, and a part of zinc ingredient is mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In settling step, the additive amount of calcium hydroxide and/or calcium oxide is not particularly limited, as long as making in leachate
Zinc conversion is the form of zinc hydroxide precipitation.Preferably, the additive amount of calcium hydroxide and/or calcium oxide is substantially matching
The content of effective carbonate in leachate, for example, the amount of the substance of calcium hydroxide and/or calcium oxide that settling step is added is leaching
Out in liquid the amount of the substance of effective carbonate 100% to 130%, more preferable 100% to 110%.Appropriately add hydroxide
Calcium and/or calcium oxide help to control process costs, it helps improve finished product zinc product grade.
In settling step, calcium hydroxide and/or calcium oxide are added into leachate, stirring is reacted, and solid is generated
Precipitating.The temperature of reaction is not particularly limited, but can carry out well since reaction is not necessarily to heating, therefore particularly preferably normal
It is reacted under temperature (such as 15~25 DEG C), it is on the one hand energy saving, on the other hand also reduce environmental pollution caused by ammonia volatilization.
Mixing time is not particularly limited, as long as being precipitated, preferably stirs 1~2 hour.
It is filtered after stirring, obtains the first solid and the first filtrate.The main component of first solid be zinc hydroxide and
Calcium carbonate.First filtrate continues on for subsequent calcium zincates synthesis.
The synthesis of step 3 calcium zincates
Calcium hydroxide and/or calcium oxide are added into the first filtrate, stirring is reacted.The hydroxide being added in this step
The ratio between amount of substance of zinc ammonium complex ion preferably 1~1.2 in the amount of the substance of calcium and/or calcium oxide and the first filtrate:2, it is more excellent
Select 1~1.1:2.Reaction temperature is not particularly limited, and can be such as 15~90 DEG C, preferably 20~90 DEG C, and further preferred 30
~60 DEG C；Or it is also preferred that 15~25 DEG C of reaction temperature, the temperature range have without heating, energy conservation and reduce ammonia volatilization
Advantage.Reaction can be filtered for 0.5~2 hour after (preferably 0.5~1 hour), without prolonged reaction and ageing process.
The second solid and the second filtrate is obtained by filtration.The main component of second solid is calcium zincates, in addition can be passed through two to the second filtrate
Then carbonoxide is recycled for the extraction containing zinc ore crude.
Step 4 is dry
The ratio of first solid and the second solid according to actual needs is mixed, in the at a temperature of drying not higher than 125 DEG C, is obtained
To finished product：Mixture containing calcium carbonate, zinc hydroxide and calcium zincates.Or the first solid and the second solid are needed as practical
The ratio mixing wanted obtains finished product in 150~350 DEG C of at a temperature of drying：Contain calcium carbonate, zinc oxide and calcium hydroxide
Mixture.The mixed proportion of first solid and the second solid can according in real work to calcium carbonate, hydroxide in mixture
The content demand of the various components such as zinc/zinc oxide, calcium zincates and determine.
In addition, in further embodiment, the higher finished product of zinc hydroxide percentage in order to obtain, step 2 (precipitating)
Step 2a (pretreatment) can be divided into, step 2b (heavy zinc) two steps carry out：
Step 2a pretreatment
In pre-treatment step, a certain amount of calcium hydroxide and/or oxygen is added in the leachate that obtains to step 1 (extraction)
Change the effective carbonate having more than needed in calcium, with leachate and form precipitation of calcium carbonate, thus by effective carbonate more than needed from leachate
Middle removing.Effective carbonate more than needed refers to effective carbonate that participation is formed except the carbonate of ammine carbonate zinc.Pretreatment
The amount of the calcium hydroxide and/or calcium oxide that are added in step can be appropriate according to the amount of effective carbonate having more than needed in leachate
Ground determines.
Such as：Effective carbonate total concentration in leachate is detected, in conjunction with leachate total volume, calculates and is participated in leachate
Ammine carbonate zinc formed carbonate except effective carbonate more than needed amount (for ammine carbonate zinc, zinc ammonium complex ion
With the amount substantially 1 of carbanion:1 relationship), then obtain to remove and partly or entirely have more than needed needed for effective carbonate in leachate
Calcium hydroxide and/or Calcium Oxide Dosage (allowing certain legitimate skew) to be added.For example, the hydroxide added in this step
The amount of the substance of calcium and/or calcium oxide can be calculated as follows：
nPretreatment=(nLeachate carbonate-nZinc ammonium complex ion)×b
Wherein, nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step, nLeachate carbonateFor
The amount of the substance of effective carbonate in leachate, nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in leachate, b is to be
Number.The value range of b can be such as 0<B≤110%：If it is desired to effective carbonate more than needed is substantially removed, then b
Value can be such as 90%≤b≤110%；If it is desired to only remove a part effective carbonate more than needed, then the value of b can
Think such as 60%≤b<90% or 30%≤b<60% or 0<b<30%.Under conditions of 90%≤b≤110%,
This technique can be made to obtain the high final product of zinc grade.
Required calcium hydroxide and/or calcium oxide are added into leachate, are filtered after being stirred to react 1~2 hour, mistake
Filter to obtain pre-treated solid and intermediate filtrate.Reaction preferably carries out under such as 15~25 DEG C of room temperature.Pre-treated solid it is main
Ingredient is calcium carbonate.Intermediate filtrate is taken to enter step 2b (heavy zinc) operation.
Step 2b sinks zinc
Calcium hydroxide and/or calcium oxide is added to the resulting intermediate filtrate of step 2a, makes carbonate/bicarbonate in filtrate
Root switchs to calcium carbonate, while zinc ammonium complex ion-zinc ion-zinc hydroxide balance moves in filtrate, part zinc ammino from
Son decomposes, and zinc ingredient is mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In step 2b, the dosage of calcium hydroxide and/or calcium oxide is not particularly limited, as long as making in the filtrate in filtrate
Carbonate/bicarbonate switch to calcium carbonate, part zinc conversion is the form of zinc hydroxide precipitation.Preferably, originally
The dosage of calcium hydroxide and/or calcium oxide matches substantially with the amount of remaining effectively carbonate in intermediate filtrate in step, such as this
The amount that the substance of remaining effective carbonate in the amount and intermediate filtrate of the substance of calcium hydroxide and/or calcium oxide is added in step is
1:1, allow certain reasonable error；But in view of equilibrium system complicated present in extraction-precipitation solution system, hydrogen can also be made
Calcium oxide and/or calcium oxide are suitably excessive, to promote fully reacting.Based on theory matching dosage, calcium hydroxide and/or oxygen
Change the excess of calcium preferably no more than 30%, if excess is excessively high, subsequent calcium zincates settling step may be caused
Adverse effect.For example, the amount of the substance of the calcium hydroxide and/or calcium oxide that add in heavy zinc step can be calculated as follows：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein, nHeavy zincFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in heavy zinc step, nLeachate carbonateTo leach
The amount of the substance of effective carbonate in liquid, nPretreatmentFor the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step
Amount, c is coefficient, the value of c preferably 100%≤c≤130%, more preferable 100%≤c≤110%.
In step 2b, required calcium hydroxide (or calcium oxide) is added into the resulting filtrate of step 2a, is stirred to react 1
~2 hours, reaction preferably carried out under such as 15~25 DEG C of room temperature.It is filtered after reaction, filtered obtained liquid
For the first filtrate, the first filtrate is used for subsequent calcium zincates synthesis step；The solid being obtained by filtration is heavy zinc solid, main
Ingredient includes zinc hydroxide and calcium carbonate.
The heavy zinc solid that pre-treated solid that step 2a (pretreatment) obtains, step 2b (heavy zinc) can be obtained with it is subsequent
The second solid that step 3 (calcium zincates synthesis) obtains according to actual needs ratio mixing, then not higher than 125 DEG C at a temperature of
It is dried, obtains finished product：The mixture of calcium carbonate, zinc hydroxide and calcium zincates；Or 150~350 DEG C at a temperature of
It is dry, obtain finished product：The mixture of calcium carbonate, zinc oxide and calcium hydroxide.What step 2b (heavy zinc) can also be obtained is heavy
The ratio mixing of the second solid that zinc solid and subsequent step 3 (calcium zincates synthesis) obtain according to actual needs, is then being not higher than
It is dried at a temperature of 125 DEG C, obtains finished product：Mixture containing calcium carbonate, zinc hydroxide and calcium zincates；Or
It is dry at a temperature of 150~350 DEG C, obtain finished product：Mixture containing calcium carbonate, zinc oxide and calcium hydroxide.Mixing ratio
Example can be determined according to the actual demand of zinc component ratio in finished product.
It is described in detail below in conjunction with embodiment of the embodiment to the disclosure, 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 11.67%, raw ore oxygenation efficiency 95.2%, the zinc ingredient in the mine are with zinc carbonate
It is primarily present form.
300 grams are taken containing zinc ore crude, is put into 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate matter
Amount concentration 5%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, filtered fluid
Middle zinc mass concentration 3.374% (calculate by zinc oxide is then 4.2%), carbonate mass concentration 6.21% in liquid, increased portion
It is divided into zinc carbonate in raw ore to bring into.According to inspection data, solvable zinc recovery is 91.11% in leaching process raw ore, and total zinc returns
Yield is 86.74%.
The zinc ammonia complexing liquid being obtained by filtration after 600 milliliters of extractions is taken, 19.69 grams of calcium oxide are added, is formed for that will participate in
Carbonate more than needed except the carbonate of ammine carbonate zinc, which sinks, to be removed, and is stirred after calcium hydroxide is added, reaction carries out after 1 hour
Filtering.500 milliliters of filtered liquid is taken, 9.29 grams of calcium hydroxides are added for depositing zinc ingredient, stirring carries out at normal temperature
Reaction, reaction are filtered after 1 hour, and the solid being obtained by filtration is calcium carbonate and zinc hydroxide mixture.
Remaining Zn content (working as meter with zinc oxide) is 15.12 gram per liters in filtered fluid, adds 2.21 grams of oxygen
It is stirred after changing calcium, reaction is filtered after 1 hour, remaining Zn content (working as meter with zinc oxide) in filtered filtrate
It is 2.3 gram per liters, the solid being obtained by filtration is mainly containing the mixture of calcium zincates.
The mixture of calcium carbonate, zinc hydroxide is merged with the mixture mainly containing calcium zincates, is done at 250 DEG C
Dry, the mixture after drying is sampled analysis, and Zn content (working as meter with zinc oxide) is 43.4% in mixture.
Embodiment 2
Chongqing somewhere zinc ore, Zn content 12.93%, raw ore oxygenation efficiency 94.82%, the zinc ingredient in the mine are with zinc silicate
It is primarily present form.
300 grams are taken containing zinc ore crude, is put into 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate matter
Measure concentration 6%) in carry out heating stirring extraction, 50 DEG C of extraction temperature, mixing time 2 hours, be then filtered, liquid after filtering
Zinc mass concentration 3.681% in body, carbonate mass concentration 6.34% in liquid, increased portion are divided into zinc carbonate in raw ore and bring into.
According to inspection data, solvable zinc recovery 90.07% in leaching process raw ore, total zinc recovery 85.41%.
The zinc ammonia complexing liquid being obtained by filtration after 600 milliliters of extractions is taken, 18.98 grams of calcium hydroxides are added, for shape will to be participated in
It removes at the carbonate more than needed except the carbonate of ammine carbonate zinc is heavy, is stirred after calcium hydroxide is added, reaction 1 hour laggard
Row filtering.It takes filtered liquid to take 500 milliliters, 10.6 grams of calcium hydroxides is added for depositing zinc composition, stir at normal temperature
It is reacted, reaction is filtered after 1 hour, and the solid being obtained by filtration is calcium carbonate and zinc hydroxide mixture.
Remaining Zn content (working as meter with zinc oxide) is 15.03 gram per liters in filtered fluid, adds 2.26 grams of oxygen
It is stirred after changing calcium, reaction is filtered after 1 hour, remaining Zn content (working as meter with zinc oxide) in filtered filtrate
It is 1.9 gram per liters, the solid being obtained by filtration is mainly containing the mixture of calcium zincates.
The mixture of calcium carbonate, zinc hydroxide is merged with the mixture mainly containing calcium zincates, is done at 250 DEG C
Dry, the mixture after drying is sampled analysis, and Zn content (working as meter with zinc oxide) is 43.3% in mixture.
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 are obvious 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 low-grade beneficiation method containing zinc ore crude, which is characterized in that the low-grade beneficiation method packet containing zinc ore crude
Include following steps：
Leach step：Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein is described
Digestion agent is the mixed aqueous solution or ammonia of ammonia and 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；
Settling step：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：Calcium hydroxide and/or calcium oxide are added into first filtrate, stirring is reacted, and is filtered
Obtain the second solid and the second filtrate；
Drying steps：Second solid is taken to be dried, or by some or all of described first solid and described second
Some or all of solid mix then drying, obtains finished product.
2. the low-grade beneficiation method containing zinc ore crude according to claim 1, which is characterized in that in the settling step
The amount of the substance of the calcium oxide and/or calcium hydroxide of addition is the amount of the substance of effective carbonate in the leachate
100% to 130%, preferably 100% to 110%.
3. the low-grade beneficiation method containing zinc ore crude according to claim 1 or 2, which is characterized in that the settling step
It is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added into the leachate that the leach step obtains, and are stirred,
Pre-treated solid and intermediate filtrate is obtained by filtration,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, is stirred, filtering,
Obtain heavy zinc solid and the first filtrate；
In the drying steps, takes the pre-treated solid, the heavy zinc solid to mix with second solid, then carry out
It is dry；Or the heavy zinc solid is taken to mix with second solid, then it is dried.
4. the low-grade beneficiation method containing zinc ore crude according to claim 3, which is characterized in that in the pre-treatment step
The calcium hydroxide of middle addition and/or the amount of calcium oxide are：
nPretreatment=(nLeachate carbonate-nZinc ammonium complex ion)×b
Wherein,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the leachate,
The value of b is 0<B≤110%, the preferably value of b are 90%≤b≤110%.
5. the low-grade beneficiation method containing zinc ore crude according to claim 3 or 4, which is characterized in that walked in the heavy zinc
The calcium hydroxide of addition and/or the amount of calcium oxide are in rapid：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein,
nHeavy zincTo sink the amount of the substance of calcium hydroxide and/or calcium oxide added in zinc step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the pre-treatment step,
The value of c is 100%≤c≤130%, and preferably the value of c is 100%≤c≤110%.
6. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 5, which is characterized in that the leaching
The mass concentration for mentioning total ammonia in agent is 5%~15%, preferably 6%~8%,
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%, and preferably the value range of a is 150%~250%.
7. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 6, which is characterized in that described
Zinc ammino in the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in calcium zincates synthesis step and first filtrate from
The ratio between amount of substance of son is 1~1.2:2, preferably 1~1.1:2.
8. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 7, which is characterized in that described
Second filtrate that calcium zincates synthesis step obtains is passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as leaching
Agent is proposed, is recycled for the extraction containing zinc ore crude.
9. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 8, it is characterised in that：
In the drying steps, not higher than 125 DEG C at a temperature of be dried, the finished product be contain calcium carbonate, hydrogen
The mixture of zinc oxide and calcium zincates；
Alternatively, in the drying steps, 150~350 DEG C at a temperature of be dried, the finished product is to contain carbonic acid
The mixture of calcium, zinc oxide and calcium hydroxide.
10. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 9, which is characterized in that described
In settling step, reacted in 15~25 DEG C of at a temperature of stirring.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817494.0A CN108866332A (en) | 2018-07-24 | 2018-07-24 | A kind of low-grade beneficiation method containing zinc ore crude |
| CN201980002306.1A CN110972482B (en) | 2018-07-24 | 2019-05-16 | Beneficiation method for low-grade zinc-containing raw ore |
| PCT/CN2019/087246 WO2020019834A1 (en) | 2018-07-24 | 2019-05-16 | Mineral processing method for low-grade zinc-containing raw ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817494.0A CN108866332A (en) | 2018-07-24 | 2018-07-24 | A kind of low-grade beneficiation method containing zinc ore crude |
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Application publication date: 20181123 |