CN108950238A - 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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- CN108950238A CN108950238A CN201810817127.0A CN201810817127A CN108950238A CN 108950238 A CN108950238 A CN 108950238A CN 201810817127 A CN201810817127 A CN 201810817127A CN 108950238 A CN108950238 A CN 108950238A
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- zinc
- carbonate
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- calcium
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- 239000011701 zinc Substances 0.000 title claims abstract description 193
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 76
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 87
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 230000008569 process Effects 0.000 claims abstract description 36
- 239000011787 zinc oxide Substances 0.000 claims abstract description 36
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 32
- 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 19
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims description 76
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 66
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 60
- 239000000920 calcium hydroxide Substances 0.000 claims description 60
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 60
- 239000000292 calcium oxide Substances 0.000 claims description 58
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 58
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 55
- 238000001556 precipitation Methods 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 43
- 239000000706 filtrate Substances 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 24
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 21
- 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
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011667 zinc carbonate Substances 0.000 claims description 17
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 17
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 235000004416 zinc carbonate Nutrition 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 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
- 238000000151 deposition Methods 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000007812 deficiency Effects 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 38
- 235000014692 zinc oxide Nutrition 0.000 description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 description 19
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 19
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 18
- 229940007718 zinc hydroxide Drugs 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 11
- 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
- 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 5
- 239000012467 final 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
- 230000000694 effects Effects 0.000 description 4
- 238000005188 flotation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 229910007661 ZnSiO3 Inorganic materials 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- FWABRVJYGBOLEM-UHFFFAOYSA-N diazanium;azane;carbonate Chemical compound N.[NH4+].[NH4+].[O-]C([O-])=O FWABRVJYGBOLEM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011363 dried mixture Substances 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
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 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
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NSEQHAPSDIEVCD-UHFFFAOYSA-N N.[Zn+2] Chemical compound N.[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-N 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
- 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
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940105847 calamine Drugs 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 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
- 230000008021 deposition 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
- 238000001035 drying Methods 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 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
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005456 ore beneficiation Methods 0.000 description 1
- 238000003672 processing method 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
- 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
- 230000002194 synthesizing effect Effects 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
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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (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, settling step, calcium zincates synthesis step, calcining step.Disclosed method realizes the economic and environment-friendly utilization of super low-grade zinc, applied widely, is not necessarily to ammonia still process, it is simple and easy to do, the energy consumption for greatly reducing technique 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 grade of the zinc oxide ore in China is low on the whole, and the average grade is less than 5%.
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 for treating zinc oxide ore at present, but regarding the flotation process of the zinc oxide ore, the foreign selection indexes of the zinc oxide ore 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 of the flotation zinc oxide, and the zinc after vulcanization coating can be directly used as a raw material for producing metal zinc or zinc oxide after secondary treatment of pyrogenic process or pressure oxidation.
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 precipitation 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 mixing part or all of the first solid and part or all of the second solid, and then calcining at 850-1050 ℃ to obtain a mixture containing zinc oxide and calcium oxide.
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 precipitation 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 provided by the further embodiment of the disclosure, the precipitation step is divided into a pretreatment step and a zinc precipitation step, and the pretreatment step and the zinc precipitation step are carried out in two steps:
a pretreatment step: adding calcium hydroxide and/or calcium oxide into the leachate obtained in the leaching step, stirring, filtering to obtain pretreated solid and intermediate filtrate,
and (3) zinc precipitation: adding calcium hydroxide and/or calcium oxide into the intermediate filtrate obtained in the pretreatment step, stirring and filtering to obtain a zinc precipitation solid and a first filtrate;
in the calcining step, the pretreatment solid, the zinc precipitation solid and the second solid are mixed and then calcined at 850-1050 ℃: or mixing the zinc precipitation solid with the second solid, and then calcining at 850-1050 ℃.
In a further embodiment of the present disclosure, there is provided a method for beneficiation of a low-grade zinc-containing raw ore, wherein the amount of calcium hydroxide and/or calcium oxide added in the pretreatment step is:
npretreatment of＝(nLeach liquor carbonate-nZinc ammonia complex ion)×b
Wherein,
npretreatment ofAs the amount of the substance of calcium hydroxide and/or calcium oxide added in the pretreatment step,
nleach liquor carbonateIs the amount of available carbonate species in the leachate,
nzinc ammonia complex ionIs the amount of the substance of the zinc ammonia complex ions in the leaching solution,
the value of b is more than 0 and less than or equal to 110 percent, and preferably, the value of b is more than or equal to 90 percent and less than or equal to 110 percent.
In a further embodiment of the present disclosure, there is provided a low grade zinc-containing raw ore beneficiation method, wherein the amount of calcium hydroxide and/or calcium oxide added in the zinc precipitation step is:
ndepositing zinc＝(nLeach liquor carbonate-nPretreatment of)×c
Wherein,
ndepositing zincThe amount of the substance of calcium hydroxide and/or calcium oxide added in the zinc precipitation step,
nleach liquor carbonateIs the amount of available carbonate species in the leachate,
npretreatment ofThe amount of the substance of calcium hydroxide and/or calcium oxide added in the pretreatment step,
c is between 100 and 130 percent, and preferably c is between 100 and 110 percent.
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 the further embodiment of the disclosure, the ratio of the amount of the substance of calcium hydroxide and/or calcium oxide added in the calcium zincate synthesis step 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 a further embodiment of the disclosure, the zinc content of the zinc-containing raw ore is 3% -15%.
In the beneficiation method of the low-grade zinc-containing raw ore, provided by a further embodiment of the disclosure, in the precipitation step, the reaction is carried out under stirring at a temperature of 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.
5) 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.
6) 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(triaminozinc carbonate),[Zn(NH3)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, "available carbonate" in a solution (including, but not limited to, various liquors such as lixiviants, leachate, intermediate filtrate, and the like) refers to the sum of carbonate and bicarbonate in the solution.
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. Precipitation of
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
Ca(OH)2+[Zn(NH3)i]CO3＝CaCO3↓+Zn(OH)2↓+iNH3
(i is an integer of 1 to 4)
[Zn(NH3)i]CO3+Ca(OH)2＝[Zn(NH3)i](OH)2+CaCO3↓
(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
Zn(OH)2＝ZnO+H2O
CaCO3＝CaO+CO2
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-containing raw ore is mixed with the leaching agent and stirred for a period of time which is not particularly limited as long as the zinc component in the raw ore is leached, and the stirring time is preferably 1 to 4 hours, 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 precipitation 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 10-50 g/L, so that the comprehensive economic benefit of the method disclosed by the invention can be optimized. Optionally, the leachate may be purified by conventional methods, if necessary.
Step 2 precipitation
In the precipitation step, calcium hydroxide and/or calcium oxide is added into the leachate containing zinc ammine complex ions to convert carbonate/bicarbonate radical in the leachate into calcium carbonate, meanwhile, the balance of zinc ammine complex ions-zinc hydroxide in the leachate is shifted, part of zinc ammine complex ions are decomposed, and part of zinc components are mainly coprecipitated with calcium carbonate in the form of zinc hydroxide.
In the precipitation step, the amount of calcium hydroxide and/or calcium oxide added is not particularly limited as long as carbonate/bicarbonate in the leachate is converted into calcium carbonate and part of the zinc component is converted into a form of zinc hydroxide precipitate. Preferably, 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 material added in the precipitation step is 100% to 130%, more preferably 100% to 110% of the amount of available carbonate material in the leach solution. Proper amount of calcium hydroxide and/or calcium oxide is added, which is helpful for controlling the process cost and improving the grade of finished zinc products.
In the precipitation step, calcium hydroxide and/or calcium oxide is added into the leaching solution, and the mixture is stirred for reaction to generate solid precipitate. The reaction temperature is not particularly limited, but since the reaction can be favorably carried out without heating, it is particularly preferable to carry out the reaction at room temperature (for example, 15 to 25 ℃ C.), on the one hand, energy can be saved, and on the other hand, environmental pollution due to volatilization of ammonia can be reduced. 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 components of the first solid are zinc hydroxide and calcium carbonate. The first filtrate still contains part of the zinc ammine complex ions and is continuously 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. 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 second solid contains calcium zincate as main component, and carbon dioxide may be introduced into the second filtrate for reuse in leaching zinc-containing raw ore. In the step, calcium zincate is synthesized in a zinc ammonia environment, and the leached zinc component is further precipitated and recovered.
Step 4 calcination
Mixing the first solid and the second solid according to an actual required proportion, drying, and calcining at 850-1050 ℃ to obtain a final product: comprises a mixture of zinc oxide and calcium oxide.
In addition, in a further embodiment, in order to obtain a mixture with a higher percentage of zinc oxide, step 2 (precipitation) can be carried out in two steps, step 2a (pretreatment), step 2b (zinc precipitation):
step 2a pretreatment
In the pretreatment step, a certain amount of calcium hydroxide and/or calcium oxide is added into the leachate obtained in the step 1 (leaching), and calcium carbonate precipitation is formed with the surplus available carbonate in the leachate, so that the surplus available carbonate is removed from the leachate. The surplus available carbonate refers to an available carbonate other than the carbonate participating in the formation of the zinc ammine carbonate. The amount of calcium hydroxide and/or calcium oxide added in the pretreatment step may be appropriately determined depending on the amount of available carbonate remaining in the leachate.
For example: detecting the total concentration of available carbonate in the leachate, calculating the amount of surplus available carbonate except carbonate participating in formation of the zinc ammonium carbonate in the leachate by combining the total volume of the leachate (for the zinc ammonium carbonate, the amount of zinc ammonium complex ions and the carbonate ions is approximately in a 1:1 relationship), and obtaining the amount of calcium hydroxide and/or calcium oxide (allowing a slight excess) required to be added for removing part or all of the surplus available carbonate in the leachate. For example, the amount of the substance of calcium hydroxide and/or calcium oxide added in the present step can be calculated as follows:
npretreatment of＝(nLeach liquor carbonate-nZinc ammonia complex ion)×b
Wherein n isPretreatment ofThe amount of the substance of calcium hydroxide and/or calcium oxide added in the pretreatment step, nLeach liquor carbonateThe amount of available carbonate in the leachate, nZinc ammonia complex ionThe amount of the zinc ammine complex ion in the leaching solution, and b is a coefficient. The value range of b may be, for example, 0<b is less than or equal to 110%: if desired, to make available surplus carbonate radicalsIn this way, the value of b can be, for example, between 90% and 110%; if it is desired to remove only a portion of the remaining available carbonate, b can be chosen, for example, from 60% ≦ b<90%, or 30% or less of b<60%, or 0<b<30 percent. Under the condition that b is more than or equal to 90% and less than or equal to 110%, the process can obtain the final product with high zinc grade.
Adding required calcium hydroxide and/or calcium oxide into the leachate, stirring for reaction for 1-2 hours, filtering, and filtering to obtain a pretreated solid and an intermediate filtrate. The reaction is preferably carried out at a normal temperature of, for example, 15 to 25 ℃. The main component of the pretreated solids was calcium carbonate. Taking the intermediate filtrate to enter the step 2b (zinc precipitation). Step 2b zinc deposition
And (2) adding calcium hydroxide and/or calcium oxide into the intermediate filtrate obtained in the step (2 a) to convert carbonate/bicarbonate radicals in the filtrate into calcium carbonate, moving the balance of zinc ammine complex ions-zinc hydroxide in the filtrate, decomposing the zinc ammine complex ions, and coprecipitating the zinc component with the calcium carbonate mainly in the form of zinc hydroxide.
In step 2b, the amount of calcium hydroxide and/or calcium oxide used is not particularly limited as long as carbonate/bicarbonate in the filtrate is converted into calcium carbonate and part of the zinc component is converted into the form of zinc hydroxide precipitate. Preferably, the amount of calcium hydroxide and/or calcium oxide used in this step substantially matches the amount of available carbonate remaining in the intermediate filtrate, e.g., the amount of calcium hydroxide and/or calcium oxide added in this step is 1:1 with the amount of available carbonate remaining in the intermediate filtrate, subject to certain tolerances; however, in view of the complex equilibrium system present in the leaching-precipitation solution system, it is also possible to make the calcium hydroxide and/or calcium oxide in a suitable excess to promote the completion of the reaction. The excess of calcium hydroxide and/or calcium oxide is preferably not more than 30% based on the theoretically matched amount, and if the excess is too high, the subsequent calcium zincate precipitation step may be adversely affected. For example, the amount of calcium hydroxide and/or calcium oxide species added in the zinc precipitation step can be calculated as follows:
ndepositing zinc＝(nLeach liquor carbonate-nPretreatment of)×c
Wherein n isDepositing zincThe amount of the substance of calcium hydroxide and/or calcium oxide added in the zinc precipitation step, nLeach liquor carbonateThe amount of available carbonate in the leachate, nPretreatment ofThe amount of the calcium hydroxide and/or calcium oxide added in the pretreatment step is C as a coefficient, and the value of c is preferably 100% to 130%, more preferably 100% to 110%.
In step 2b, the filtrate obtained in step 2a is added with the required calcium hydroxide and/or calcium oxide, and stirred for reaction for 1-2 hours, preferably at normal temperature of 15-25 ℃. Filtering after the reaction, wherein the filtered liquid is a first filtrate, and the first filtrate is used for the subsequent calcium zincate synthesis step; the solid obtained by filtering is zinc precipitation solid, and the main components of the solid comprise zinc hydroxide and calcium carbonate.
The pretreatment solid obtained in the step 2a, the zinc precipitation solid obtained in the step 2b and the second solid obtained in the subsequent step 3 (calcium zincate synthesis) can be mixed according to the actual required proportion, and then the mixture is calcined at 850-1050 ℃ to obtain the final product: comprises a mixture of zinc oxide and calcium oxide. Or mixing the zinc precipitation solid obtained in the step 2b (zinc precipitation) and the second solid obtained in the subsequent step 3 (calcium zincate synthesis) according to an actual required proportion, and then calcining at 850-1050 ℃ to obtain a final product: comprises a mixture of zinc oxide and calcium oxide. The mixing ratio can be determined according to the actual requirement for the ratio of zinc oxide in the final product.
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 zinc ore in some places in Yunnan province is 11.67%, the oxidation rate of raw ore is 95.2%, and the zinc component in the ore takes zinc carbonate as a main existing form.
300 g of zinc-containing raw ore is taken and put into 900 ml of ammonia-ammonium carbonate mixed solution (the mass concentration of total ammonia is 10 percent and the mass concentration of carbonate is 5 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the mass concentration of zinc in the filtered liquid is 3.374 percent (4.2 percent calculated by zinc oxide), the mass concentration of carbonate in the liquid is 6.21 percent, and the increased part is brought 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 91.11%, and the total recovery rate of zinc is 86.74%.
Taking 600 ml of zinc-ammonia complex liquid obtained by leaching and filtering, adding 19.69 g of calcium oxide for precipitating surplus carbonate except the carbonate participating in the formation of zinc ammonium carbonate, adding calcium hydroxide, stirring, reacting for 1 hour, and filtering. And taking 500 ml of filtered liquid, adding 9.29 g of calcium hydroxide for precipitating zinc components, stirring at normal temperature for reaction, filtering after the reaction is carried out for 1 hour, and filtering to obtain a solid which is a mixture of calcium carbonate and zinc hydroxide.
The remaining zinc content (in terms of zinc oxide equivalent) in the filtered liquid was 15.12 g/l, 2.21 g of calcium oxide was added thereto and stirred, and after reacting for 1 hour, filtration was carried out with the zinc content (in terms of zinc oxide equivalent) in the filtrate being 2.3 g/l, and the solid obtained by filtration was a mixture mainly containing calcium zincate.
The mixture of calcium carbonate and zinc hydroxide was combined with the mixture containing mainly calcium zincate, dried at 105 c, and the dried mixture was calcined at 950 c for 2 hours, and sampled for analysis, the zinc oxide content of the mixture being 55.2%.
Example 2
In the zinc ore in Chongqing, the zinc content is 12.93%, the oxidation rate of raw ore is 94.82%, 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 carbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 6 percent) to be heated, stirred and leached, the leaching temperature is 50 ℃, the stirring time is 2 hours, then the filtering is carried out, the mass concentration of zinc in the filtered liquid is 3.681 percent, the mass concentration of carbonate in the liquid is 6.34 percent, and the increased part is brought 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 90.07%, and the recovery rate of total zinc is 85.41%.
Taking 600 ml of zinc-ammonia complex solution obtained by leaching and filtering, adding 18.98 g of calcium hydroxide for precipitating surplus carbonate except the carbonate participating in the formation of zinc ammonium carbonate, adding the calcium hydroxide, stirring, reacting for 1 hour, and filtering. And taking 500 ml of filtered liquid, adding 10.6 g of calcium hydroxide for precipitating zinc components, stirring at normal temperature for reaction, filtering after the reaction is carried out for 1 hour, and filtering to obtain a solid which is a mixture of calcium carbonate and zinc hydroxide.
The remaining zinc content (in terms of zinc oxide equivalent) in the filtered liquid was 15.03 g/l, 2.26 g of calcium oxide was added thereto and stirred, and after reacting for 1 hour, filtration was carried out with the zinc content (in terms of zinc oxide equivalent) in the filtrate being 1.9 g/l, and the solid obtained by filtration was a mixture mainly containing calcium zincate.
The mixture of calcium carbonate and zinc hydroxide was combined with the mixture containing mainly calcium zincate, dried at 105 c, and the dried mixture was calcined at 950 c for 2 hours, and sampled for analysis to have a zinc oxide content of 54.7% in the mixture.
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 (10)
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 precipitation 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 mixing part or all of the first solid and part or all of the second solid, and then calcining at 850-1050 ℃ to obtain a mixture containing zinc oxide and calcium oxide.
2. A process according to claim 1, wherein the amount of calcium oxide and/or calcium hydroxide added in the precipitation step is 100% to 130%, preferably 100% to 110% of the amount of available carbonate species in the leach solution.
3. The beneficiation method for low-grade zinc-containing raw ore according to claim 1 or 2, wherein the precipitation step is performed in two steps of pretreatment and zinc precipitation:
a pretreatment step: adding calcium hydroxide and/or calcium oxide into the leachate obtained in the leaching step, stirring, filtering to obtain pretreated solid and intermediate filtrate,
and (3) zinc precipitation: adding calcium hydroxide and/or calcium oxide into the intermediate filtrate obtained in the pretreatment step, stirring and filtering to obtain a zinc precipitation solid and a first filtrate;
in the calcining step, the pretreatment solid, the zinc precipitation solid and the second solid are mixed and then calcined at 850-1050 ℃: or mixing the zinc precipitation solid with the second solid, and then calcining at 850-1050 ℃.
4. The beneficiation process of a low grade zinc-containing raw ore according to claim 3, wherein the amount of calcium hydroxide and/or calcium oxide added in the pretreatment step is:
npretreatment of＝(nLeach liquor carbonate-nZinc ammonia complex ion)×b
Wherein,
npretreatment ofAs the amount of the substance of calcium hydroxide and/or calcium oxide added in the pretreatment step,
nleach liquor carbonateIs the amount of available carbonate species in the leachate,
nzinc ammonia complex ionIs the amount of the substance of the zinc ammonia complex ions in the leaching solution,
the value of b is more than 0 and less than or equal to 110 percent, and preferably, the value of b is more than or equal to 90 percent and less than or equal to 110 percent.
5. The beneficiation method of a low-grade zinc-containing raw ore according to claim 3 or 4, wherein the amount of calcium hydroxide and/or calcium oxide added in the zinc precipitation step is:
ndepositing zinc＝(nLeach liquor carbonate-nPretreatment of)×c
Wherein,
ndepositing zincThe amount of the substance of calcium hydroxide and/or calcium oxide added in the zinc precipitation step,
nleach liquor carbonateIs the amount of available carbonate species in the leachate,
npretreatment ofThe amount of the substance of calcium hydroxide and/or calcium oxide added in the pretreatment step,
c is between 100 and 130 percent, and preferably c is between 100 and 110 percent.
6. A process for beneficiation of low grade zinc containing raw ore according to any one of claims 1 to 5, characterized in that the mass concentration of total ammonia in the leaching agent 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%.
7. The beneficiation method for a low-grade zinc-containing raw ore according to any one of claims 1 to 6, wherein a ratio of an amount of a substance of calcium hydroxide and/or calcium oxide added in the calcium zincate synthesis step to an amount of a substance of zinc ammine complex ion in the first filtrate is 1 to 1.2:2, preferably 1 to 1.1: 2.
8. The beneficiation method for low-grade zinc-containing raw ore according to any one of claims 1 to 7, 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.
9. The beneficiation method for low-grade zinc-containing raw ore according to any one of claims 1 to 8, wherein the zinc content of the zinc-containing raw ore is 3% to 15%.
10. The beneficiation method for low-grade zinc-containing raw ore according to any one of claims 1 to 9, wherein in the precipitation step, the reaction is performed with stirring at a temperature of 15 to 25 ℃.
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| CN201810817127.0A CN108950238A (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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| CN114150156A (en) * | 2021-11-30 | 2022-03-08 | 西安建筑科技大学 | Process for extracting zinc from low-grade zinc-containing dust and preparing nano zinc oxide |
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| CN114150156A (en) * | 2021-11-30 | 2022-03-08 | 西安建筑科技大学 | Process for extracting zinc from low-grade zinc-containing dust and preparing nano zinc oxide |
| CN114150156B (en) * | 2021-11-30 | 2023-10-13 | 西安建筑科技大学 | Low-grade zinc-containing dust zinc extraction and nano zinc oxide preparation process |
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