CN108950240A - 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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- CN108950240A CN108950240A CN201810817164.1A CN201810817164A CN108950240A CN 108950240 A CN108950240 A CN 108950240A CN 201810817164 A CN201810817164 A CN 201810817164A CN 108950240 A CN108950240 A CN 108950240A
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- zinc
- carbonate
- raw ore
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- 239000011701 zinc Substances 0.000 title claims abstract description 149
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000002386 leaching Methods 0.000 claims abstract description 75
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 230000008569 process Effects 0.000 claims abstract description 37
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 26
- 239000000920 calcium hydroxide Substances 0.000 claims description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 26
- 239000000292 calcium oxide Substances 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 24
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 21
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 18
- 239000001099 ammonium carbonate Substances 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000011667 zinc carbonate Substances 0.000 claims description 18
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 18
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 17
- 235000004416 zinc carbonate Nutrition 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 235000010755 mineral Nutrition 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000005261 decarburization Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 13
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 29
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000004110 Zinc silicate Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000019352 zinc silicate Nutrition 0.000 description 5
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 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
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005188 flotation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229940007718 zinc hydroxide Drugs 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 229910007661 ZnSiO3 Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 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
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 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
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- SRONXGSXMGLHAE-UHFFFAOYSA-N C(O)(O)=O.N[Zn]N Chemical compound C(O)(O)=O.N[Zn]N SRONXGSXMGLHAE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- MUHUIJPSGRCRFX-UHFFFAOYSA-M [Zn+].C([O-])([O-])=O.[NH4+] Chemical compound [Zn+].C([O-])([O-])=O.[NH4+] MUHUIJPSGRCRFX-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940105847 calamine Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HYJPZWOFVGWLCA-UHFFFAOYSA-N diazanium zinc carbonate Chemical compound [Zn].[NH4+].C([O-])([O-])=O.[NH4+] HYJPZWOFVGWLCA-UHFFFAOYSA-N 0.000 description 1
- HHICRQHZPBOQPI-UHFFFAOYSA-L diazanium;zinc;dicarbonate Chemical compound [NH4+].[NH4+].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O HHICRQHZPBOQPI-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction 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
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
-
- 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
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
This disclosure relates to a kind of low-grade beneficiation method containing zinc ore crude, including leach step, decarbonation process, calcium zincates synthesis step, calcining step.Disclosed method is by wet-leaching in conjunction with ore-dressing technique, 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, 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 the deficiency of secondary treatment technical process after solution 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 comprehensive technical field of inorganic chemical industry and mineral processing technology, relates to resource utilization of low-grade zinc-containing raw ore, and particularly relates to a mineral processing method of low-grade zinc-containing raw ore.
Background
The production and consumption of zinc in China are at the top of the world, domestic zinc resources cannot meet the production, and a large amount of zinc raw materials need to be imported every year. China is a country with abundant zinc oxide resources, and the reserve of zinc metal in zinc oxide ores in China is about 2800 ten thousand tons, which accounts for about 27.7 percent of the reserve of zinc metal in the zinc oxide ores in the world. The zinc oxide ore in China is low in zinc grade on the whole, the average grade is less than 5%, the reserves of dead ore and lean ore which cannot be economically utilized at present account for the vast majority, and mining tailings containing 3-5% of zinc oxide and billions of tons of the mining tailings are stockpiled.
Therefore, the method has important strategic significance for effectively developing and utilizing low-grade zinc oxide ore resources and relieving the problem of insufficient supply of domestic zinc raw materials.
The main process for utilizing the low-grade zinc oxide ore comprises the following steps: the production of the zinc hypoxide by the pyrogenic process is limited by national industrial policies due to the high energy consumption and high pollution of the process.
Flotation is the main process of the low-grade zinc oxide ore at present, but regarding the zinc oxide flotation process, the foreign zinc oxide ore sorting indexes are as follows: the zinc grade is 36-40%, the recovery rate is 60-70%, and the highest recovery rate is 78%; the selection indexes of the zinc oxide ore in China are as follows: the zinc grade is 35-38%, the recovery rate is 68% on average, and the highest recovery rate is 73%. Therefore, the problems of low ore dressing recovery rate, low concentrate grade and the like are common problems existing in the ore dressing of zinc oxide ores at home and abroad, a large amount of sodium sulfide needs to be added for vulcanization treatment in the flotation of zinc oxide, and zinc sulfide can be directly used as a raw material for producing metal zinc or zinc oxide after being treated by a pyrogenic process, so that the energy consumption is high and the pollution is serious.
As for the wet extraction of zinc ore, sulfuric acid leaching, calcium chloride, ammonium chloride, etc. are mainly known in the prior art. The sulfuric acid leaching method has low selectivity, can leach a large amount of soluble silicon in the ore, the generated colloidal silicon is difficult to filter, and the acid leaching method generates a large amount of sulfate slag, so that great environmental protection treatment pressure is caused; the sulfuric acid leaching can not treat the zinc silicate and zinc ferrite components in the ore. The calcium chloride method cannot effectively treat leaching of components such as zinc silicate, zinc ferrite and the like in raw ores, and has the disadvantages of unsatisfactory leaching rate, high-temperature leaching and poor comprehensive economic benefit. In the ammonium chloride process, however, the recovery of zinc from the leachate after leaching the crude ore is very difficult and is not suitable for industrial use.
Therefore, the existing process cannot satisfactorily utilize the low-grade zinc-containing raw ore.
Disclosure of Invention
Problems to be solved by the invention
The existing process for utilizing low-grade zinc ores has the problems of high energy consumption, low ore dressing recovery rate, serious environmental pollution, low economic value and the like. The invention solves the problems existing in the utilization of low-grade zinc ores by improving the zinc ore treatment process.
Means for solving the problems
In order to solve the problems in the prior art, the invention provides a beneficiation method of low-grade zinc-containing raw ore, which comprises the following steps:
leaching: mixing and stirring ground zinc-containing raw ore and a leaching agent, and then filtering to obtain a leaching agent, wherein the leaching agent is a mixed aqueous solution of ammonia and ammonium bicarbonate, or a mixed aqueous solution of ammonia and ammonium carbonate, or a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate;
a decarburization step: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
calcium zincate synthesis step: adding calcium hydroxide and/or calcium oxide into the first filtrate, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
and (3) calcining: and drying the second solid, and then calcining at 650-1050 ℃ to decompose calcium zincate contained in the second solid into zinc oxide and calcium oxide.
In a further embodiment of the present disclosure, there is provided a process for beneficiation of a low grade zinc-containing raw ore, wherein the mass concentration of total ammonia in the lixiviant is 5% to 15%, preferably 6% to 8%,
the mole concentration of available carbonate in the leaching agent is as follows:
Clixiviant carbonate radical＝(nTotal zinc of raw ore-nRaw mineral zinc carbonate)×a/VLixiviant
Wherein,
Clixiviant carbonate radicalIs the molar concentration of available carbonate in the leaching agent,
ntotal zinc of raw oreIs the amount of the zinc element in the zinc-containing raw ore,
nraw mineral zinc carbonateIs the amount of zinc carbonate material in the zinc-bearing raw ore,
VlixiviantIs the volume of the leaching agent,
the value range of a is 100-600%, preferably 150-250%.
In the beneficiation method of the low-grade zinc-containing raw ore, provided by a further embodiment of the disclosure, the concentration of zinc ammine complex ions (based on the mass of zinc element) in the leachate obtained in the leaching step is 10g/L or more, and preferably 10-25 g/L.
In the beneficiation method of the low-grade zinc-containing raw ore, in the leaching step, the concentration (based on the mass of zinc element) of zinc ammine complex ions in the obtained leachate is adjusted to be 10-25 g/L.
In a further embodiment of the present disclosure there is provided a process for the beneficiation of a low grade zinc containing raw ore, wherein the amount of the species of calcium oxide and/or calcium hydroxide added in the decarbonisation step is from 100% to 130%, preferably from 100% to 110%, of the amount of the species of available carbonate in the leachate.
In the beneficiation method of the low-grade zinc-containing raw ore, in the calcium zincate synthesis step, the ratio of the amount of the substance of calcium hydroxide and/or calcium oxide to the amount of the substance of zinc ammine complex ions in the first filtrate is 1-1.2: 2, preferably 1-1.1: 2.
In the beneficiation method of the low-grade zinc-containing raw ore provided by the further embodiment of the disclosure, carbon dioxide is introduced into the second filtrate obtained in the calcium zincate synthesis step, and the second filtrate introduced with the carbon dioxide is used as a leaching agent and is recycled for leaching of the zinc-containing raw ore.
In the beneficiation method of the low-grade zinc-containing raw ore provided by the further embodiment of the disclosure, the reaction temperature of the calcium zincate synthesis step is 15-90 ℃, preferably 30-60 ℃, or preferably 15-25 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
The present disclosure achieves the following advantageous technical effects in one or more aspects:
1) the wet leaching and the ore dressing process are combined, so that the economic and environment-friendly utilization of the ultralow-grade zinc ore is realized.
2) The method disclosed by the invention is wide in application range, and the ammonia-ammonium bicarbonate leaching system can be used for effectively extracting and utilizing zinc-containing raw ores in various forms.
3) The method breaks the inherent method that the traditional ammonia-ammonium bicarbonate method zinc complex leaching process destroys the complex environment by heating and evaporating ammonia to realize zinc ion crystallization separation, creatively adds calcium oxide or calcium hydroxide into an ammonium bicarbonate-zinc ammonia complex system to shift the balance of zinc ammine complex ion-zinc hydroxide, realizes the selective crystallization separation of zinc element by a balance shift principle on the premise of not destroying the ammonia dissolving liquid environment, and avoids the phenomenon that the prior ammonia heating and evaporating method destroys the ammonia environment to cause the coprecipitation of a large amount of impurities. The process disclosed by the invention is simple and easy to implement without ammonia distillation, greatly reduces the energy consumption of the process, and also avoids the problems in various aspects such as water treatment pressure, high-temperature and high-pressure potential safety hazards, equipment corrosion, extra environment-friendly treatment burden caused by evaporation and volatilization of a large amount of ammonia and the like caused by ammonia distillation.
4) Compared with a zinc oxide flotation process, the method disclosed by the invention solves the problems of process recovery rate and quality grade of fine products, and overcomes the defect that the raw material after vulcanization treatment needs a secondary treatment process.
6) The method disclosed by the invention has the advantages that the pollution is small, the auxiliary materials can be recycled, and the problem of environmental pollution caused by the auxiliary raw materials of the existing zinc oxide treatment process is solved.
7) The method realizes the synthesis of calcium zincate in the zinc ammonia environment for the first time, and the reaction selectivity for synthesizing the calcium zincate from zinc ammonia complex ions is high, simple and rapid.
Detailed Description
Various exemplary embodiments, features and aspects of the disclosure are described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. In some instances, methods, means, reagents and devices well known to those skilled in the art are not described in detail, but those skilled in the art can implement the technical solutions of the present disclosure based on the general knowledge in the art.
The application range of the method disclosed by the invention is not particularly limited, and the method can be widely applied to the utilization of various zinc-containing raw ores. The advantages of the process disclosed herein are particularly pronounced when low grade zinc-bearing raw ore is used as a production feedstock. For example, the low-grade zinc-containing raw ore can be zinc-containing raw ore with the zinc content of 3-15%; particularly, before the method, a large amount of zinc-containing raw ores (lean ores and mill tailings) with the zinc content of 3% -6% are stockpiled, the existing various processes cannot utilize the economic value of the zinc-containing raw ores, and great processing pressure is caused.
In the present disclosure, the form of the presence of the zinc component in the zinc-containing raw ore is not particularly limited, for example, the zinc component may be present in one or more forms including, but not limited to, zinc oxide, zinc carbonate, zinc silicate, and the like.
Noun interpretation
As used herein, unless otherwise specified, "zinc ammine carbonate" is a generic term for compounds formed from zinc ammine complex ions and carbonate ions, and includes [ Zn (NH)3)4]CO3(Zinc tetraammine carbonate), [ Zn (NH)3)3]CO3(Triammine Zinc carbonate), [ Zn (NH)3)2]CO3(Diaminozinc carbonate), [ Zn (NH)3)]CO3(zinc monoammonium carbonate), and the like.
In this context, unless otherwise stated, "zinc ammine complex ion" is a generic term for each level of ammine zinc complex ion, and includes [ Zn (NH)3)4]2+(Zinc tetraammine ion), [ Zn (NH)3)3]2+(Triammine Zinc ion), [ Zn (NH)3)2]2+(Diaminato zinc ion), [ Zn (NH)3)]2+(zinc ion ammine), and the like.
As used herein, unless otherwise indicated, "carbonate" in a solution (including but not limited to various liquors such as lixiviants, leachate, and the like) refers to the sum of carbonate and bicarbonate in the solution.
"optional" or "optionally" means that the subsequently described step may or may not be performed, and that the expression includes instances where the subsequently described step is performed and instances where the subsequently described step is not performed.
Chemical reaction formula
1. Leaching
a. Zinc oxide leaching
Extracting agent of ammonia and ammonium bicarbonate
ZnO+(i-1)NH3+NH4HCO3＝[Zn(NH3)i]CO3+H2O (i is an integer of 1 to 4)
Ammonia and ammonium carbonate as leaching agents
ZnO+(i-2)NH3+(NH4)2CO3＝[Zn(NH3)i]CO3+H2O (i is an integer of 2 to 4)
b. Leaching of zinc hydroxide
Extracting agent of ammonia and ammonium bicarbonate
Zn(OH)2+(i-1)NH3+NH4HCO3＝[Zn(NH3)i]CO3+2H2O
(i is an integer of 1 to 4)
Ammonia and ammonium carbonate as leaching agents
Zn(OH)2+(i-2)NH3+(NH4)2CO3＝[Zn(NH3)i]CO3+2H2O
(i is an integer of 2 to 4)
c. Zinc carbonate (calamine) leaching
ZnCO3+iNH3＝[Zn(NH3)i]CO3(i is an integer of 1 to 4)
d. Zinc silicate leaching
Extracting agent of ammonia and ammonium bicarbonate
ZnSiO3+(i-1)NH3+NH4HCO3＝[Zn(NH3)i]CO3+H2O+SiO2
(i is an integer of 1 to 4)
Ammonia and ammonium carbonate as leaching agents
ZnSiO3+(i-2)NH3+(NH4)2CO3＝[Zn(NH3)i]CO3+H2O+SiO2
(i is an integer of 2 to 4)
2. Decarburization of carbon
Reaction of lime with water
CaO+H2O＝Ca(OH)2
Precipitation of
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↓
(i is an integer of 1 to 4)
Possible side reactions:
Ca(OH)2+[Zn(NH3)i]CO3＝CaCO3↓+Zn(OH)2↓+iNH3
(i is an integer of 1 to 4)
3. Calcium zincate synthesis
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O＝Ca(OH)2·2Zn(OH)2·2H2O+2iNH3
(i is an integer of 1 to 4)
4. Calcination of
Ca(OH)2·2Zn(OH)2·2H2O＝CaO+2ZnO+5H2O
The concrete process steps
Step 1 extraction
Mixing the ground low-grade zinc-containing raw ore with a prepared leaching agent according to a certain proportion, and stirring and leaching. The leaching agent may be selected from: a mixed aqueous solution of ammonia and ammonium bicarbonate; a mixed aqueous solution of ammonia and ammonium carbonate; a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate.
The concentration of total ammonia and the concentration of available carbonate in the leaching agent are not particularly limited, and those skilled in the art can select the concentration according to the actual needs by combining the factors such as raw ore components, grade and the like.
In the preferred scheme, the mass concentration of the total ammonia in the leaching agent is 5-15%, more preferably 6-8%, and the preferred concentration range can achieve sufficient leaching effect and avoid the problems of waste and environmental protection caused by excessive ammonia.
In a preferred scheme, the amount of available carbonate in the leaching agent is increased by 0-500% on the basis of the difference obtained by subtracting the amount of carbonate introduced by zinc carbonate in the raw material from the theoretical consumption of carbonate in complexed zinc, and more preferably, the amount of available carbonate in the leaching agent is increased by 50% -150% on the basis of the difference obtained by subtracting the amount of carbonate introduced by zinc carbonate in the raw material from the theoretical consumption of carbonate in complexed zinc. The consumption of carbonate in the theory of complex zinc is the consumption of carbonate which is used for completely converting zinc element in raw ore into zinc ammonium carbonate. Thus, the molar concentration of available carbonate in the lixiviant can be calculated as follows:
Clixiviant carbonate radical＝(nTotal zinc of raw ore-nRaw mineral zinc carbonate)×a/VLixiviant
Wherein, CLixiviant carbonate radicalIs the molar concentration of available carbonate in the lixiviant, nTotal zinc of raw oreIs the amount of material containing zinc element in the zinc raw ore, nRaw mineral zinc carbonateIs the amount of zinc carbonate in the zinc-containing raw ore, VLixiviantIs the volume of the leaching agent, a is a coefficient, and the value of a is 100 to 600 percent, preferably 150 to 250 percent. The mass concentration of carbonate in the lixiviant can be converted according to the molar concentration.
The optimized effective carbonate concentration of the leaching agent can ensure that zinc in raw ore is completely leached, can realize the circulation of carbonate in the process, and can avoid the pressure of excessive carbonate on the subsequent process treatment.
The weight ratio of the leaching agent to the zinc-containing raw ore powder is not particularly limited as long as the zinc component can be leached. Preferably, the weight ratio of the leaching agent to the zinc-containing raw ore powder is 3:1 to 5:1, so that a satisfactory leaching effect can be obtained, and the waste of the leaching agent is avoided.
The leaching temperature is not particularly limited as long as the zinc component in the raw ore is leached. Preferably leaching is carried out at normal temperature, for example leaching is carried out at 15-30 ℃; the leaching may also be carried out at slightly elevated temperatures (e.g., 30-55 ℃). The temperature can be selected according to actual conditions.
The zinc oxide raw ore and the leaching agent are mixed and stirred, and the stirring time is not particularly limited as long as the zinc component in the raw ore is leached, and is preferably 1 to 4 hours, and more preferably 1 to 2 hours.
During leaching, zinc element in raw ore is converted into zinc ammine complex ions (mainly zinc ammine complex ions at each level) and enters into a liquid phase. And filtering after leaching to obtain a leaching solution containing zinc-ammonia complex ions, wherein the leaching solution can be used for the subsequent decarburization process. The concentration of zinc ammine complex ions in the leachate is not particularly limited, but the concentration of zinc ammine complex ions (based on the mass of zinc element) in the leachate is preferably more than 10g/L, more preferably 10-25 g/L, so that the comprehensive economic benefit of the method disclosed by the invention can be optimized. If the concentration of the zinc ammine complex ions in the original leached liquid is not in the preferred range, optionally concentrating or diluting the leached liquid, and adjusting the concentration of the zinc ammine complex ions in the leachate to be in the preferred range of 10-25 g/L. Optionally, the leachate may be purified by known methods, if necessary.
Step 2 decarburization
In the decarbonization step, calcium hydroxide and/or calcium oxide are added into the leachate containing zinc-ammonia complex ions, and the available carbonate in the leachate is converted into calcium carbonate. If the concentration of the zinc ammine complex ions in the leachate is too high, equilibrium shift of zinc ammine complex ions-zinc hydroxide in the leachate may occur at the same time, and a very small portion of the zinc component may be co-precipitated with calcium carbonate in the form of zinc hydroxide.
In the decarbonising step, the amount of calcium hydroxide and/or calcium oxide added substantially matches the amount of available carbonate in the leach solution, for example, the amount of calcium hydroxide and/or calcium oxide species added in the decarbonising step is 100% to 130%, more preferably 100% to 110% of the amount of available carbonate species in the leach solution. Proper addition of calcium hydroxide and/or calcium oxide is helpful for controlling the process cost and improving the purity and quality of the finished zinc product.
In the decarbonization step, calcium hydroxide and/or calcium oxide are added into the leaching solution, and the mixture is stirred for reaction to generate solid precipitate. The reaction temperature is not particularly limited, and it is particularly preferable to carry out the reaction at room temperature (for example, 15 to 25 ℃), which not only saves energy but also reduces environmental pollution caused by ammonia volatilization. The stirring time is not particularly limited as long as a precipitate is obtained, and stirring is preferably performed for 1 to 2 hours.
And filtering after stirring to obtain a first solid and a first filtrate. The main component of the first solid is calcium carbonate which can be calcined into calcium oxide and carbon dioxide for recycling. The first filtrate continues to be used for the subsequent calcium zincate synthesis.
Step 3 calcium zincate Synthesis
And adding calcium hydroxide and/or calcium oxide into the first filtrate, and stirring for reaction. In the step, calcium zincate is synthesized in a zinc ammonia environment, and the leached zinc component is precipitated and recovered.
The ratio of the amount of the calcium hydroxide and/or calcium oxide to the amount of the zinc ammine complex ion in the first filtrate is preferably 1 to 1.2:2, more preferably 1 to 1.1: 2. The reaction temperature is not particularly limited, and may be, for example, 15 to 90 ℃, preferably 20 to 90 ℃, and more preferably 30 to 60 ℃; or the reaction temperature of 15-25 ℃ is also preferably selected, and the temperature range has the advantages of no need of heating, energy conservation and reduction of ammonia volatilization. Filtering can be carried out after the reaction is carried out for 0.5-2 hours (preferably 0.5-1 hour), and long-time reaction and ageing processes are not needed. Filtering to obtain a second solid and a second filtrate. The main component of the second solid is calcium zincate, and generally, the calcium zincate component can account for more than 95 percent of the total mass of the second solid; the second solid may also contain a small amount of co-precipitated compounds such as lead, iron, manganese, etc., depending on the starting materials, whether or not the purification step is performed, how the purification step is performed, etc. Carbon dioxide may additionally be passed to the second filtrate and then recycled for leaching of zinc containing raw ore.
Step 4 calcination
And drying the second solid, and then calcining at 650-1050 ℃ to decompose the calcium zincate into zinc oxide and calcium oxide.
Embodiments of the present disclosure will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The zinc content of the zinc ore in some places in Yunnan province is 5.6%, the oxidation rate of raw ore is 96.3%, and the zinc component in the ore takes zinc carbonate as a main existing form.
300 g of zinc oxide raw ore is taken and put into 900 ml of ammonia-ammonium bicarbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 3 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc (calculated by zinc oxide equivalent) in the filtered liquid is 1.632 percent, the mass concentration of carbonate in the liquid is 4.23 percent, and the increased part is introduced by zinc carbonate in the raw ore. According to the test data, the recovery rate of soluble zinc in the raw ore in the leaching process is 90.79%, and the total recovery rate of zinc is 87.43%.
And adding 14.55 g of calcium oxide into 600 ml of zinc-ammonia complex solution obtained by leaching and filtering for precipitating carbonate, reacting for 1 hour, and filtering. Taking 500 ml of filtered liquid, adding 2.41 g of calcium hydroxide for synthesizing calcium zincate, stirring at normal temperature for reaction, filtering after 1 hour of reaction, drying the filtered solid at 105 ℃, calcining at 950 ℃ for 2 hours, and then sampling and analyzing. The calcined product contained 71.26% zinc oxide.
Example 2
In the zinc ore in Chongqing, the zinc content is 4.7%, the oxidation rate of raw ore is 95.52%, and the zinc component in the ore takes zinc silicate as a main existing form.
300 g of zinc-containing raw ore is taken and put into 900 ml of ammonia-ammonium bicarbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 3 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc (calculated by zinc oxide equivalent) in the filtered liquid is 1.367 percent, the mass concentration of carbonate in the liquid is 3.54 percent, and the part of the zinc-containing raw ore is added by zinc carbonate in the raw ore. According to the test data, the recovery rate of soluble zinc in the raw ore in the leaching process is 91.35%, and the total recovery rate of zinc is 87.26%.
Taking 600 ml of zinc-ammonia complex liquid obtained by leaching and filtering, adding 12.18 g of calcium oxide for precipitating carbonate, reacting for 1 hour, and filtering. Taking 500 ml of filtered liquid, adding 1.99 g of calcium hydroxide for synthesizing calcium zincate, stirring at normal temperature for reaction, filtering after 1 hour of reaction, drying the filtered solid at 105 ℃, calcining at 950 ℃ for 2 hours, and then sampling and analyzing. The calcined product contained 71.08% zinc oxide.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (8)
1. The beneficiation method of the low-grade zinc-containing raw ore is characterized by comprising the following steps:
leaching: mixing and stirring ground zinc-containing raw ore and a leaching agent, and then filtering to obtain a leaching agent, wherein the leaching agent is a mixed aqueous solution of ammonia and ammonium bicarbonate, or a mixed aqueous solution of ammonia and ammonium carbonate, or a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate;
a decarburization step: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
calcium zincate synthesis step: adding calcium hydroxide and/or calcium oxide into the first filtrate, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
and (3) calcining: and drying the second solid, and then calcining at 650-1050 ℃ to decompose calcium zincate contained in the second solid into zinc oxide and calcium oxide.
2. A process for the beneficiation of a low grade zinc containing raw ore according to claim 1, wherein the mass concentration of total ammonia in the lixiviant is 5% to 15%, preferably 6% to 8%,
the mole concentration of available carbonate in the leaching agent is as follows:
Clixiviant carbonate radical＝(nTotal zinc of raw ore-nRaw mineral zinc carbonate)×a/VLixiviant
Wherein,
Clixiviant carbonate radicalIs the molar concentration of available carbonate in the leaching agent,
ntotal zinc of raw oreIs the amount of the zinc element in the zinc-containing raw ore,
nraw mineral zinc carbonateIs the amount of zinc carbonate material in the zinc-bearing raw ore,
VlixiviantIs the volume of the leaching agent,
the value range of a is 100-600%, preferably 150-250%.
3. The beneficiation method for low-grade zinc-containing raw ore according to claim 1 or 2, wherein the concentration of zinc ammine complex ions (in terms of the mass of zinc element) in the leachate obtained in the leaching step is 10g/L or more, preferably 10 to 25 g/L.
4. The beneficiation method for low-grade zinc-containing raw ore according to claim 1 or 2, wherein in the leaching step, the concentration (in terms of the mass of zinc element) of zinc ammine complex ions in the obtained leachate is adjusted to 10 to 25 g/L.
5. The process for beneficiation of low grade zinc containing raw ore according to any one of claims 1 to 4, wherein the amount of the substance of calcium oxide and/or calcium hydroxide added in the decarbonation step is 100% to 130%, preferably 100% to 110%, of the amount of the substance of available carbonate in the leachate.
6. The beneficiation method for a low-grade zinc-containing raw ore according to any one of claims 1 to 5, wherein in the calcium zincate synthesis step, a ratio of an amount of a substance of calcium hydroxide and/or calcium oxide to an amount of a substance of a zinc ammine complex ion in the first filtrate is 1 to 1.2:2, preferably 1 to 1.1: 2.
7. The beneficiation method for low-grade zinc-containing raw ore according to any one of claims 1 to 6, wherein carbon dioxide is introduced into the second filtrate obtained in the calcium zincate synthesis step, and the second filtrate introduced with carbon dioxide is recycled for leaching of the zinc-containing raw ore as a leaching agent.
8. The beneficiation method for low-grade zinc-containing raw ore according to any one of claims 1 to 7, wherein the reaction temperature of the calcium zincate synthesis step is 15 to 90 ℃, preferably 30 to 60 ℃, or preferably 15 to 25 ℃.
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| CN201810817164.1A CN108950240A (en) | 2018-07-24 | 2018-07-24 | A kind of low-grade beneficiation method containing zinc ore crude |
| PCT/CN2019/087246 WO2020019834A1 (en) | 2018-07-24 | 2019-05-16 | Mineral processing method for low-grade zinc-containing raw ore |
| CN201980002306.1A CN110972482B (en) | 2018-07-24 | 2019-05-16 | Beneficiation method for low-grade zinc-containing raw ore |
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