CN113388743A - Method for selectively extracting cobalt and nickel from nickel sulfide concentrate - Google Patents
Method for selectively extracting cobalt and nickel from nickel sulfide concentrate Download PDFInfo
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- CN113388743A CN113388743A CN202110680991.2A CN202110680991A CN113388743A CN 113388743 A CN113388743 A CN 113388743A CN 202110680991 A CN202110680991 A CN 202110680991A CN 113388743 A CN113388743 A CN 113388743A
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- sulfide concentrate
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 181
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000012141 concentrate Substances 0.000 title claims abstract description 171
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000010941 cobalt Substances 0.000 title claims abstract description 58
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 58
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002386 leaching Methods 0.000 claims abstract description 179
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 123
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- 238000000605 extraction Methods 0.000 claims abstract description 93
- 229910052742 iron Inorganic materials 0.000 claims abstract description 71
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 35
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 33
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 33
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 32
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 31
- 239000010452 phosphate Substances 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 17
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 17
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 17
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 80
- 238000000498 ball milling Methods 0.000 claims description 52
- 239000012074 organic phase Substances 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- -1 iron ions Chemical class 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000004137 mechanical activation Methods 0.000 claims description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001447 ferric ion Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 24
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 22
- 239000002893 slag Substances 0.000 abstract description 16
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000012716 precipitator Substances 0.000 abstract description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract 1
- 230000001965 increasing effect Effects 0.000 description 46
- 230000000694 effects Effects 0.000 description 20
- 239000002184 metal Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 238000013386 optimize process Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YFLLTMUVNFGTIW-UHFFFAOYSA-N nickel;sulfanylidenecopper Chemical compound [Ni].[Cu]=S YFLLTMUVNFGTIW-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a method for selectively extracting cobalt and nickel from nickel sulfide concentrate, which comprises the following steps: selectively leaching metal elements in the nickel sulfide concentrate by a mechanical activation-microbubble leaching process to obtain a nickel sulfide concentrate leaching solution, wherein the metal elements at least comprise copper, iron, cobalt, nickel, magnesium and calcium elements; adding phosphate to the nickel sulphide concentrate leachate to produce iron phosphate slag and phosphate slag precipitate, thereby removing iron and copper ions from the leachate; adding sodium fluoride as a precipitator to perform precipitation reaction so as to remove calcium ions and magnesium ions in the leachate; cobalt ions and nickel ions are respectively separated by extraction process extraction to prepare and obtain a cobalt sulfate product and a nickel sulfate product. The method not only realizes the high-efficiency recycling of the nickel element in the nickel sulfide concentrate, but also further utilizes other metal elements to reduce the pollution to the environment, and is beneficial to improving the resource utilization rate and the utilization value of raw materials.
Description
Technical Field
The invention belongs to the technical field of nickel sulfide concentrate utilization, and particularly relates to a method for selectively extracting cobalt and nickel from nickel sulfide concentrate.
Background
Nickel is an important strategic metal resource, and is widely applied to the fields of aerospace, military and civil industries due to good ductility, mechanical properties and chemical stability. In recent years, with the rapid development of the high-nickel ternary lithium battery industry, the market demand of nickel is rapidly increased. Among nickel mineral resources, polymetallic nickel sulfide concentrate is one of the most important nickel ore resources, and has a very important position in nickel resources in China and even in the world. At present, the nickel sulfide concentrate resource in the nickel ore resource which is globally explored accounts for about 40 percent. In recent years, an ultra-large magma copper-nickel sulfide ore deposit is found in the Ha-wood area in summer of Qinghai province in China, 106 million tons (average grade of 0.7%) of metal nickel of 332+333 grade is proved, and 21.77 million tons (average grade of 0.166%) of 333 grade copper resource and 3.81 million tons (average grade of 0.025%) of cobalt resource are associated, so that the ultra-large magma copper-nickel sulfide ore deposit becomes the second large nickel deposit in China. The discovery of the ultra-large nickel ore effectively relieves the current situation of the shortage of nickel resource markets in China. With the gradual development and utilization stage of the Hazaki copper-nickel sulfide ore, the development of a green and efficient nickel sulfide concentrate extraction technology has very important significance.
The common treatment methods for nickel ores comprise a pyrometallurgical process and a hydrometallurgical process, and the utilization of nickel sulfide concentrate leachate obtained by leaching nickel sulfide concentrate by a wet method in the prior art still has a plurality of problems: (1) the leaching solution of the nickel sulfide concentrate contains various metal elements such as Fe, Ni, Cu, Co and the like, and the problem still needs to be solved how to remove impurities from metal impurities in the leaching solution so as to realize the recycling of the nickel element and the cobalt element; (2) iron elements rich in nickel sulfide concentrate cause high concentration of iron ions in leachate in a wet leaching process, and the recovery process flow and energy consumption of nickel are seriously influenced; (3) how to further utilize other metal elements to reduce the pollution to the environment in the process of preparing the nickel sulfate by utilizing the leaching solution is still a problem which needs to be solved urgently. Therefore, a comprehensive utilization method of nickel sulfide concentrate needs to be further explored, which not only can remove impurities from metal impurities in the leaching solution so as to recycle nickel elements and cobalt elements, but also can further utilize other metal elements in the process of preparing nickel sulfate so as to reduce the pollution of the nickel sulfate to the environment.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for selectively extracting cobalt and nickel from nickel sulfide concentrate, which can not only solve the problem that metal impurities in a leaching solution of the nickel sulfide concentrate influence the recycling of nickel element and cobalt element, but also further utilize other metal elements in the process of preparing nickel sulfate so as to reduce the pollution of the nickel sulfate to the environment.
In order to achieve the above object, the present invention provides a method for selectively extracting cobalt and nickel from a nickel sulfide concentrate, comprising:
s10, placing the nickel sulfide concentrate into a ball mill for ball milling treatment, and performing mechanical activation treatment on the nickel sulfide concentrate to form activated nickel sulfide concentrate;
s20, placing the activated nickel sulfide concentrate into a leaching solution, introducing gas into the leaching solution to form micro bubbles, and stirring to leach metal elements in the activated nickel sulfide concentrate to obtain a nickel sulfide concentrate leachate, wherein the metal elements at least comprise copper, iron, cobalt, nickel, magnesium and calcium elements;
s30, removing iron by a phosphate method, comprising the following steps: adding an oxidant to the nickel sulphide concentrate leachate to oxidize ferrous ions in the leachate to ferric ions to form a first solution; adding phosphate into the first solution to enable iron ions and copper ions in the first solution to react respectively to generate precipitates, and performing solid-liquid separation to remove the precipitates to obtain a liquid-phase second solution;
wherein the oxidant is selected from any one of hydrogen peroxide, sodium chlorate, sodium hypochlorite, ammonium persulfate and sodium persulfate; adding phosphate to perform precipitation reaction, wherein the reaction temperature is 60-80 ℃, the reaction time is 30-120 min, and the end point pH is controlled to be 2-3 in the reaction process;
s40, adding sodium fluoride serving as a precipitating agent into the second solution to enable magnesium ions and calcium ions in the second solution to have a precipitation reaction, and after the reaction is finished, carrying out solid-liquid separation to obtain a liquid-phase third solution;
s50, preparing an extraction organic phase containing a P507 extraction agent, taking the third solution as an extraction water phase, extracting and separating cobalt ions through an extraction process, and separating to obtain a loaded organic phase and a nickel-containing raffinate after extraction is finished;
s60, carrying out back extraction on the loaded organic phase to obtain cobalt-containing back extraction liquid, and preparing a cobalt sulfate product by taking the cobalt-containing back extraction liquid as a raw material;
s70, preparing and obtaining a nickel sulfate product by taking the nickel-containing raffinate as a raw material.
Preferably, the process conditions of the ball milling treatment in the step S10 include: the ball milling strength is 7.5G-15G, the ball-material ratio is 15: 1-30: 1, and the ball milling time is 120 min-240 min; the particle size range of the activated nickel sulfide concentrate after ball milling is that D50 is less than or equal to 15 mu m.
Preferably, in the step S20, the leaching solution is a sulfuric acid solution, the usage amount of the sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.20mL/g to 0.40mL/g, the gas introduced into the leaching solution is oxygen, the introduction flow rate of the oxygen is 0.6L/min to 1.0L/min, the leaching time of the activated nickel sulfide concentrate is 240min to 360min, the leaching temperature is 80 ℃ to 100 ℃, and the end-point pH in the leaching process is 1 to 3.
Preferably, the step S40 specifically includes: and (2) placing the second solution in a constant-temperature water bath, stirring, adding a sodium carbonate solution to enable the second solution to reach a preset pH value, adding sodium fluoride serving as a precipitating agent into the second solution, carrying out precipitation reaction on magnesium ions and calcium ions in the second solution and the sodium fluoride, and carrying out solid-liquid separation after the reaction is finished to obtain a liquid-phase third solution.
Further preferably, in the step S40, the temperature of the constant-temperature water bath is 70 ℃ to 100 ℃, and the predetermined pH value is 4 to 5; and the excess coefficient of the amount of the sodium fluoride is 1.25-2.0 based on the amount of the magnesium ions and the calcium ions in the second solution which are completely precipitated.
Preferably, in the step S50,
firstly, preparing an extraction organic phase containing a P204 extraction agent, taking the third solution as an extraction water phase, removing impurities through an extraction process, and separating after extraction to obtain a third solution after impurity removal;
then, the extraction organic phase containing the P507 extraction agent is used for carrying out extraction separation on cobalt ions on the third solution after impurity removal.
Preferably, the step S60 specifically includes:
washing the loaded organic phase by using a sulfuric acid solution with the concentration of 0.1-0.4 mol/L;
carrying out back extraction on the washed loaded organic phase by using a sulfuric acid solution with the concentration of 1.0-2.0 mol/L to obtain a cobalt sulfate solution;
and heating, evaporating and concentrating the cobalt sulfate solution, and then cooling and crystallizing to obtain the cobalt sulfate product.
Preferably, the step S70 specifically includes:
adding a sodium hydroxide solution into the nickel-containing raffinate, controlling the temperature of the reaction solution to be 80-100 ℃, controlling the pH value of the reaction solution to be 9-10, and performing solid-liquid separation after the reaction to obtain solid-phase nickel hydroxide precipitate;
dissolving the nickel hydroxide precipitate by using a sulfuric acid solution to obtain a nickel sulfate solution; controlling the reaction temperature to be 50-80 ℃, controlling the pH value of the reaction solution to be 3-4, and obtaining the nickel concentration in the nickel sulfate solution to be 80-100 g/L;
and (3) heating, evaporating and concentrating the nickel sulfate solution at 90-100 ℃ until the concentration of nickel is more than 300g/L, and then cooling, cooling and crystallizing to obtain a nickel sulfate product.
The method for selectively extracting cobalt and nickel from nickel sulfide concentrate provided by the invention has the following beneficial effects:
(1) the leaching method comprises the steps of leaching metal elements of nickel sulfide concentrate by using a mechanical activation-microbubble leaching process, wherein the mechanical activation is adopted to pretreat the nickel sulfide concentrate in the leaching process, so that the reaction activity of the nickel sulfide concentrate is improved, and microbubbles are introduced to enhance oxidation to control leaching and precipitation behaviors of iron in the leaching process, so that the valuable metal nickel, cobalt and copper in the nickel sulfide concentrate are efficiently leached under the normal pressure condition, and the leaching of the iron is inhibited;
(2) the method utilizes a phosphate method to carry out deep iron removal, effectively removes iron impurities in the nickel sulfide concentrate leachate, and solves the problem that iron ions with higher concentration have influence on the recovery process flow and energy consumption of nickel, wherein the loss of nickel element and cobalt element is below 2%;
(3) the metal impurities in the nickel sulfide concentrate leachate are removed, nickel sulfate is prepared to utilize nickel elements, and the separated main metal elements such as cobalt and the like can be further utilized, so that the resource utilization rate is improved.
In conclusion, the method not only realizes the high-efficiency recycling of the nickel element and the cobalt element in the nickel sulfide concentrate, but also further recycles other metal elements, is favorable for improving the utilization value of raw materials and reducing the pollution of the raw materials to the environment.
Drawings
Fig. 1 is a flow chart of a method for selectively extracting cobalt and nickel from a nickel sulfide concentrate according to an embodiment of the present invention;
FIG. 2 shows lg [ M ] in leachate of nickel sulfide concentrate provided by the embodiment of the invention]TGraph relating to pH value;
FIG. 3 is a graph showing the results of the effect of the shot-to-shot ratio on leaching of activated nickel sulfide concentrate in example 1 of the present invention;
FIG. 4 is a graph showing the results of the effect of ball milling strength (G value) on leaching of activated nickel sulfide concentrate in example 1 of the present invention;
FIG. 5 is a graph showing the results of the effect of ball milling time on leaching of activated nickel sulfide concentrate in example 1 of the present invention;
FIG. 6 is a graph showing the effect of end point pH on leaching of activated nickel sulfide concentrate in the leaching process of example 1 of the present invention;
FIG. 7 is a graph showing the effect of sulfuric acid usage on leaching of activated nickel sulfide concentrate in example 1 of the present invention;
FIG. 8 is a graph showing the relationship between pH and the ion removal rate of each metal ion in the nickel sulfide concentrate leachate during the reaction of adding phosphate to generate iron phosphate precipitate according to example 2 of the present invention;
FIG. 9 is a phase characterization (XRD) pattern of the iron phosphate slag according to example 2 of the present invention;
FIG. 10 is a graph showing the relationship between the end point pH and the removal rate of calcium ions and magnesium ions from the leachate of nickel sulfide concentrate in example 3 according to the present invention;
FIG. 11 is a graph showing the relationship between the reaction temperature and the removal rate of calcium ions and magnesium ions from the leachate of nickel sulfide concentrate in example 3 according to the present invention;
fig. 12 is a graph showing the relationship between the excess factor of the amount of sodium fluoride used and the removal rate of calcium ions and magnesium ions from the leachate of nickel sulfide concentrate in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention provides a method for selectively extracting cobalt and nickel from nickel sulfide concentrate, and the method comprises the following steps of referring to figure 1:
and step S10, placing the nickel sulfide concentrate into a ball mill for ball milling treatment, and performing mechanical activation treatment on the nickel sulfide concentrate to form activated nickel sulfide concentrate.
Preferably, the process conditions of the ball milling treatment include: the ball milling strength is 7.5G-15G, the ball-material ratio is 15: 1-30: 1, and the ball milling time is 120 min-240 min; the particle size range of the activated nickel sulfide concentrate after ball milling is that D50 is less than or equal to 15 mu m.
Further preferably, the ball milling strength is 10G, the ball-to-material ratio is 20:1, and the ball milling time is 180 min.
The ball milling medium is formed by mixing stainless steel grinding balls or zirconium grinding balls with different diameters, and the diameters and the corresponding masses of the grinding balls are respectively as follows:
(0.5kg)，
(0.5kg)，
(0.25kg)。
by adopting mechanical activation to pretreat the nickel sulfide concentrate, the mineral structure of the nickel sulfide concentrate is destroyed, and the reaction activity of the nickel sulfide concentrate is improved, thereby being beneficial to improving the leaching efficiency of metal elements in the nickel sulfide concentrate.
And step S20, placing the activated nickel sulfide concentrate into leaching solution, introducing gas into the leaching solution to form micro bubbles, and stirring to leach metal elements in the activated nickel sulfide concentrate to obtain nickel sulfide concentrate leachate, wherein the metal elements at least comprise copper, iron, cobalt, nickel, magnesium and calcium elements.
Preferably, the leaching solution is a sulfuric acid solution, the dosage of the sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.20-0.40 mL/g, the gas introduced into the leaching solution is oxygen, the introduction flow rate of the oxygen is 0.6-1.0L/min, the leaching time of the activated nickel sulfide concentrate is 240-360 min, the leaching temperature is 80-100 ℃, and the end point pH value in the leaching process is 1-3.
Further preferably, the usage amount of the sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/g, the gas introduced into the leaching solution is oxygen, the introduction flow rate of the oxygen is 0.8L/min, the leaching time of the activated nickel sulfide concentrate is 300min, and the leaching temperature is 90 ℃.
Preferably, the stirring is carried out by mechanical stirring, and the stirring speed is 200rpm to 400 rpm.
Magnetic stirring or mechanical stirring can be selected as the stirring mode, but the influence of the dynamic condition on the leaching process is obvious, and the phenomena of insufficient stirring dynamics, incomplete stirring and the like exist in the magnetic stirring process, so that the mechanical stirring is favorable for enhancing the dynamics of the reaction process and improving the leaching efficiency of metal elements in the leaching process.
According to the invention, on the basis of mechanical activation treatment of the nickel sulfide concentrate, microbubble is introduced to enhance oxidation to control leaching and precipitation of iron in the leaching process, so that selective and efficient leaching of the nickel sulfide concentrate under normal pressure is realized, and leaching of iron is inhibited.
Step S30, removing iron by using a phosphate method, comprising the following steps: adding an oxidant to the nickel sulphide concentrate leachate to oxidize ferrous ions in the leachate to ferric ions to form a first solution; and adding phosphate into the first solution to enable iron ions and copper ions in the first solution to respectively react to generate precipitates, and performing solid-liquid separation to remove the precipitates to obtain a liquid-phase second solution.
Preferably, the oxidant is selected from any one of hydrogen peroxide, sodium chlorate, sodium hypochlorite, ammonium persulfate and sodium persulfate.
Preferably, the excess coefficient of the amount of the oxidant is 3-4 based on the amount of the ferrous ions in the leachate completely oxidized into the ferric ions.
Preferably, the phosphate is phosphate-containing salt such as trisodium phosphate, triammonium phosphate and the like.
Further preferably, the excess coefficient of the amount of the phosphate is 1 based on the amount that allows complete precipitation of iron ions and copper ions in the first solution.
Preferably, in the process of adding phosphate for precipitation reaction, the reaction temperature is 60-80 ℃, the reaction time is 30-120 min, and the end point pH is controlled to be 2-3 in the reaction process.
Wherein the precipitate is iron phosphate slag and copper phosphate slag.
The solubility of ferric sulfate in solution is very low, and the solubility product Ksp of ferric phosphate is 1.3 × 10-27The iron phosphate precipitate can be selectively precipitated by controlling the conditions such as the dosage of phosphate, the pH value of the reaction, the reaction time and the like, and the iron removal principle of the phosphate precipitation method is as follows:
Fe2++1/2H2O2+H+→Fe3++H2O
Fe3++PO4 3-→FePO4↓
FIG. 2 shows M in the leachaten+-PO4 3--H2O is lg [ M ]]TGraph relating to pH value, wherein M is metal ion, lg [ M ]]TIs the concentration logarithm value of metal ions in the reaction system]T＝0.01mol/L。
As can be seen from fig. 2, nickel, cobalt, copper, iron can be precipitated in the form of phosphate in a certain range, wherein iron phosphate precipitation can be obtained in a lower pH range. When the pH value is 2-3, the iron ions with the valence of 3 in the solution can be removed to 10- 3.8mol/L～10-5.6mol/L (8.88 ppm-0.14 ppm), theoretically, the iron ions in the leaching solution can be removed completely; when the pH value is 2.0, the equilibrium concentration of copper ions in the solution is 0.035g/L, which indicates that when the phosphate method is used for removing iron, copper ions can be removed together, so that when the iron phosphate method is used, the copper ions in the solution need to be removed firstly.
And step S40, adding sodium fluoride serving as a precipitating agent into the second solution to enable magnesium ions and calcium ions in the second solution to have a precipitation reaction, and after the reaction is finished, performing solid-liquid separation to obtain a liquid-phase third solution.
Preferably, the step S40 specifically includes: and (2) placing the second solution in a constant-temperature water bath, stirring, adding a sodium carbonate solution to enable the second solution to reach a preset pH value, adding sodium fluoride serving as a precipitating agent into the second solution, carrying out precipitation reaction on magnesium ions and calcium ions in the second solution and the sodium fluoride, and carrying out solid-liquid separation after the reaction is finished to obtain a liquid-phase third solution.
The principle of removing calcium and magnesium from the leachate by using sodium fluoride is as follows:
Ca2++2F-→CaF2↓，Ksp＝2.7×10-11
Mg2++2F-→MgF2↓，Ksp＝6.5×10-9
preferably, the temperature of the constant-temperature water bath is 70-100 ℃, and the preset pH value is 4-5; and the excess coefficient of the amount of the sodium fluoride is 1.25-2.0 based on the amount of the magnesium ions and the calcium ions in the second solution which are completely precipitated.
Further preferably, the temperature of the constant-temperature water bath is 90 ℃, and the preset pH value is 4.5; the excess factor of the amount of sodium fluoride was 1.5 based on the amount of magnesium ions and calcium ions in the second solution completely precipitated.
In order to achieve the best calcium and magnesium removal efficiency, excessive sodium fluoride needs to be added, but if the excessive coefficient of the amount of the sodium fluoride is too large, the amount of the sodium fluoride is increased continuously, the calcium and magnesium removal efficiency is not increased obviously, and F in the solution is caused-The ions are excessive and new impurities are generated.
Calcium fluoride and magnesium fluoride are generated in the process of precipitating calcium and magnesium by sodium fluoride, and effective collision among molecules is increased along with the increase of temperature, so that precipitates are easily formed; and, high temperature favors Ca2+、Mg2+The enrichment of the ions enables the ions to be more effectively gathered together to form a large-particle precipitate, and the formed large-particle precipitate can cause Ca2+、Mg2+Ions are adsorbed on the surface of the filter material to promote precipitation of precipitates, so that calcium fluoride and magnesium fluoride are easy to form colloid if the temperature is too high, and the problems of long filtering process time, difficult filtering, metal ion adsorption and the like are caused.
And step S50, preparing an extraction organic phase containing a P507 extraction agent, taking the third solution as an extraction water phase, extracting and separating cobalt ions through an extraction process, and separating after extraction is finished to obtain a loaded organic phase and a nickel-containing raffinate.
Preferably, the step S50 specifically includes:
and S501, preparing an extraction organic phase containing a P204 extracting agent, taking the third solution as an extraction water phase, removing impurities through an extraction process, and separating after extraction to obtain a third solution after impurity removal.
Preferably, the volume fraction of the P204 extractant in the extracted organic phase is 20-30%, the saponification rate of the P204 extractant is 50-60%, the extraction ratio is 1: 1-2: 1, the extraction temperature is 20-30 ℃, the extraction time is 10-20 min, the standing time is 10-20 min, and the pH value in the reaction process is controlled to be 3-4.
Further preferably, the volume fraction of the P204 extractant in the extracted organic phase is 20%, the saponification rate of the P204 extractant is 60%, the extraction phase ratio is 1:1, the extraction temperature is 25 ℃, the extraction time is 10min, the standing time is 10min, and the pH in the reaction process is controlled to be 3.5.
Preferably, the P204 extractant is used for removing trace amounts of copper, iron, and aluminum metal impurities in the third solution.
Step S502, carrying out extraction separation of cobalt ions on the third solution after impurity removal by using the extraction organic phase containing the P507 extraction agent:
preparing an extraction organic phase containing a P507 extraction agent, taking the impurity-removed third solution as an extraction water phase, extracting and separating cobalt ions through an extraction process, and separating after extraction is finished to obtain a loaded organic phase and a nickel-containing raffinate.
Preferably, the volume fraction of the P507 extracting agent in the extracted organic phase is 20-30%, the saponification rate of the P507 extracting agent is 70-80%, the extraction ratio is 1.5: 1-3: 1, the extraction temperature is 20-30 ℃, the extraction time is 10-20 min, the standing time is 10-20 min, and the pH value in the reaction process is controlled to be 3-4.
Further preferably, the volume fraction of the P507 extracting agent in the extracted organic phase is 25%, the saponification rate of the P507 extracting agent is 70%, the extraction phase ratio is 2:1, the extraction temperature is 25 ℃, the extraction time is 10min, the standing time is 10min, and the pH value in the reaction process is controlled to be 3.25.
And step S60, carrying out back extraction on the loaded organic phase to obtain cobalt-containing back extraction liquid, and preparing cobalt sulfate products by taking the cobalt-containing back extraction liquid as a raw material.
Preferably, the step S60 specifically includes:
step S601, washing the loaded organic phase by using a sulfuric acid solution with the concentration of 0.1-0.4 mol/L.
And step S602, carrying out back extraction on the washed loaded organic phase by using a sulfuric acid solution with the concentration of 1.0-2.0 mol/L to obtain a cobalt sulfate solution.
Preferably, the concentration of the sulfuric acid solution is 2mol/L, the stripping time is 20min, and the extraction phase ratio (O/A) is 2.5: 1.
and S603, heating, evaporating and concentrating the cobalt sulfate solution, and then cooling, cooling and crystallizing to obtain the cobalt sulfate product.
Preferably, the heating temperature is 90-100 ℃, the temperature for cooling is 50-60 ℃, and the crystallization time is 2-3 h.
Further preferably, the heating temperature is 90 ℃, the cooling temperature is 58 ℃, and the crystallization time is 2 h.
And step S70, preparing and obtaining a nickel sulfate product by taking the nickel-containing raffinate as a raw material.
Preferably, the S70 specifically includes:
and step S701, adding a sodium hydroxide solution into the nickel-containing raffinate, and performing solid-liquid separation after the reaction is finished to obtain solid-phase nickel hydroxide precipitate.
Preferably, the temperature of the reaction solution is controlled to be 80-100 ℃, the pH value of the reaction solution is controlled to be 9-10, the mass fraction of the sodium hydroxide solution is 5-15%, and the reaction time is 3-5 h.
Further preferably, the temperature of the reaction solution is controlled to be 90 ℃, the pH value of the reaction solution is controlled to be 9, the mass fraction of the sodium hydroxide solution is 10%, and the reaction time is 4 hours.
And S702, dissolving the nickel hydroxide precipitate by using a sulfuric acid solution to obtain a nickel sulfate solution.
Preferably, the reaction temperature is controlled to be 50-80 ℃, the pH value of the reaction solution is controlled to be 3-4, the reaction time is 3-5 h, and the concentration of nickel in the nickel sulfate solution is 80-100 g/L.
Further preferably, the reaction temperature is controlled to be 60 ℃, the pH value of the reaction solution is controlled to be 3.5-3.6, the reaction time is 4 hours, and the concentration of nickel in the nickel sulfate solution is 100 g/L.
And S703, heating, evaporating and concentrating the nickel sulfate solution, and then cooling and crystallizing to prepare a nickel sulfate product.
Preferably, the heating temperature is controlled to be 90-100 ℃, the nickel sulfate solution is concentrated until the concentration of nickel is more than 300g/L, the temperature is controlled to be reduced to 50-60 ℃, and the pH value in the reaction process is controlled to be 3-4.
Further preferably, the heating temperature is controlled to be 90 ℃, the temperature for cooling is controlled to be 53 ℃, and the pH value in the reaction process is controlled to be 3.5-3.6.
The nickel element in the nickel sulfide concentrate can be recycled by preparing the nickel sulfate product.
The above-described method for selectively extracting cobalt and nickel from a nickel sulfide concentrate will be described below with reference to specific examples, and it will be understood by those skilled in the art that the following examples are specific examples of the above-described method for selectively extracting cobalt and nickel from a nickel sulfide concentrate of the present invention, and are not intended to limit the entirety thereof.
The nickel sulfide concentrate according to the embodiment of the present invention is provided by Qinghai yellow river mining company, and the main components and the phase analysis of the nickel sulfide concentrate are shown in tables 1 and 2.
Table 1: main metal component of nickel sulfide concentrate
Table 2: full element semi-quantitative analysis (XRF) of nickel sulfide concentrate
Example 1: preparation of nickel sulfide concentrate leachate
Step one, placing the nickel sulfide concentrate into a ball mill for ball milling treatment, and performing mechanical activation treatment on the nickel sulfide concentrate to form activated nickel sulfide concentrate.
And step two, placing the activated nickel sulfide concentrate into a sulfuric acid solution, introducing oxygen into the sulfuric acid solution to form micro bubbles, and stirring to leach metal elements in the activated nickel sulfide concentrate to obtain a nickel sulfide concentrate leachate, wherein the metal elements at least comprise copper, iron, cobalt, nickel, magnesium and calcium elements.
(1) Investigating the influence of ball material ratio on preparing nickel sulfide concentrate leaching solution
Wherein the reaction conditions are selected as follows: the ball milling strength is 10G, the ball milling time is 180min, the dosage of a sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/G, the introduction flow of oxygen is 0.8L/min, the magnetic stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 300min, and the leaching temperature is 90 ℃; the leaching of the activated nickel sulfide concentrate under the conditions of ball-to-material ratios of 10:1, 15:1, 20:1, 25:1 and 30:1 is respectively considered. Fig. 3 is a graph showing the effect of shot ratio on leaching of activated nickel sulfide concentrate, and the experimental results obtained under the above conditions are shown in fig. 3.
As can be seen from FIG. 3, the leaching efficiency of Ni, Co and Cu is gradually increased with the increase of the ball-to-material ratio, while the leaching efficiency of Fe is reduced from 50% to 42% when the ball-to-material ratio is increased from 10:1 to 15:1, and then the leaching efficiency of Fe is kept basically unchanged by continuously increasing the ball-to-material ratio. When the ball-to-feed ratio is 20:1, the leaching rates of nickel, cobalt, copper and iron are 96.1%, 95.6%, 92.2% and 43.7%, respectively. In conclusion, the ball-to-material ratio is preferably 15: 1-30: 1; when the ball-material ratio is 20: when 1, the metal selective leaching effect of the activated nickel sulfide concentrate is the best.
(2) Investigating the influence of the ball milling strength (G value) on the preparation of the nickel sulfide concentrate leaching solution
Wherein the reaction conditions are selected as follows: the ball milling time is 180min, the ball-to-material ratio is 20:1, the dosage of the sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/g, the introduction flow of oxygen is 0.8L/min, the magnetic stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 300min, and the leaching temperature is 90 ℃; the leaching of the activated nickel sulfide concentrate under the conditions of 5G, 7.5G, 10G, 12.5G and 15G of ball milling strength (G value) is respectively considered. Fig. 4 is a graph showing the effect of ball milling strength (G value) on leaching of activated nickel sulfide concentrate, and the experimental results obtained under the above conditions are shown in fig. 4.
As can be seen from fig. 4, under the condition of keeping other experimental conditions unchanged, when the ball milling strength is increased from the 5G value to the 10G value, the leaching rates of nickel, cobalt and copper are increased from 72.4%, 45.2% and 76.6% to 96.1%, 94.75% and 92.15%, the ball milling strength is continuously increased, the leaching rates of nickel, cobalt and copper are not increased basically, and the leaching rates of iron are reduced and then tend to be balanced along with the increase of the ball milling strength. In summary, the ball milling strength (G value) is preferably 7.5G-15G, and when the ball milling strength is 10G value, the metal selective leaching effect of the activated nickel sulfide concentrate is the best.
(3) Investigating the influence of the ball milling time on the preparation of the nickel sulfide concentrate leaching solution
Wherein the reaction conditions are selected as follows: the ball milling strength is 10G, the ball-to-material ratio is 20:1, the dosage of a sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/G, the introduction flow of oxygen is 0.8L/min, the magnetic stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 300min, the leaching temperature is 90 ℃, and the leaching of the activated nickel sulfide concentrate under the conditions that the ball milling time is 60min, 120min, 180min and 240min is respectively considered. Fig. 5 is a graph showing the results of the effect of ball milling time on leaching of activated nickel sulphide concentrate, and the experimental results obtained under the above conditions are shown in fig. 5.
As can be seen from fig. 5, the ball milling time has no significant effect on leaching of the activated nickel sulfide concentrate under the condition that other experimental conditions are kept unchanged, and as the ball milling time is increased from 60min to 240min, the leaching rates of nickel, cobalt and copper in the nickel sulfide concentrate are increased from 88.3%, 79.1% and 76.2% to 97.8%, 95.3% and 93.4%, while the leaching of iron is not substantially affected by the ball milling time. Therefore, in view of the above, the ball milling time is preferably 120min to 240min, and 180min is most preferably selected.
(4) Investigating the influence of the end point pH value of the leaching process on the preparation of the nickel sulfide concentrate leaching solution
Wherein the reaction conditions are selected as follows: the ball milling strength is 10G, the ball-material ratio is 20:1, the ball milling time is 180min, the oxygen introduction flow rate is 1L/min, the magnetic stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 300min, the leaching temperature is 80 ℃, and the leaching of the activated nickel sulfide concentrate is respectively considered under the condition that an ammonia water solution with the initial concentration of 1mol/L and an ammonium sulfate solution with the initial concentration of 1mol/L are adopted as leaching solutions. Fig. 6 is a graph showing the effect of end-point pH on leaching of activated nickel sulphide concentrate, and the experimental results obtained under the above conditions are shown in fig. 6.
As can be seen from FIG. 6, the ammonia water solution with the initial concentration of 1mol/L and the ammonium sulfate solution with the initial concentration of 1mol/L are used as leaching solutions, the initial pH of the leaching solution is 8.5, but the pH of the leaching solution gradually decreases and is finally acidic along with the progress of the reaction, because S in the activated sulfide ore is oxidized into sulfuric acid along with the continuous oxidation of oxygen in the leaching process, and OH in the consumption solution is oxidized into sulfuric acid-The generation amount of the sulfuric acid is increased along with the continuous reaction of the ions, so that the solution is gradually in an acidic system. When the pH value of the end point of the reaction is 4.2, the leaching rates of nickel, cobalt, copper and iron in the nickel sulfide concentrate are all less than 10 percent; the leaching rates of nickel, cobalt and copper are gradually increased along with the reduction of the end point pH, and when the end point pH is 2.8, the leaching rates of nickel, cobalt and copper are 82.5%, 81.9% and 48.5% respectively, and the leaching rate of iron is only 9.7% at the moment; when the end point pH continued to decrease to 1.0, the leaching rates for nickel and cobalt did not change substantially and the leaching rates for copper and iron increased rapidly. Therefore, in order to ensure the leaching efficiency of inhibiting iron in the leaching process and improve the leaching efficiency of nickel, cobalt and copper, the pH value of the end point of the leaching process needs to be controlled to be 1-3.
(5) Influence of sulphuric acid dosage on preparation of nickel sulphide concentrate leachate
Wherein the reaction conditions are selected as follows: the ball milling strength is 7.5G, the ball-to-material ratio is 15:1, the ball milling time is 120min, the flow rate of oxygen is 0.6L/min, the magnetic stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 240min, and the leaching of the activated nickel sulfide concentrate under the condition that the sulfuric acid dosage is increased from 0.075ml/G to 0.30ml/G is respectively considered under the condition that the leaching temperature is 70 ℃. Fig. 7 is a graph showing the effect of the amount of sulfuric acid on leaching of activated nickel sulfide concentrate, and the experimental results obtained under the above conditions are shown in fig. 7.
As can be seen from FIG. 7, the dosage of sulfuric acid is increased from 0.075ml/g to 0.30ml/g, the pH value at the end point of the leaching process is between 1.5 and 2.5, and at this time, the leaching rate of nickel and cobalt is less changed with the increase of the dosage of sulfuric acid, while the leaching rate of iron is increased from 19.3% to 48.2%, and the leaching rate of copper is increased from 49.2% to 71.8%, therefore, the dosage of sulfuric acid is preferably 0.2ml/g to 0.4ml/g, and the dosage of sulfuric acid is selected as 0.3ml/g to be optimal, considering the leaching efficiency of nickel, cobalt and copper and the leaching efficiency of iron.
(6) Investigating the influence of the leaching temperature on the preparation of the nickel sulfide concentrate leaching solution
Wherein the reaction conditions are selected as follows: the ball milling strength is 10G, the ball-to-material ratio is 20:1, the ball milling time is 180min, the dosage of a sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/G, the introduction flow of oxygen is 0.8L/min, the mechanical stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 300min, the end-point pH value of the leaching process is 2.5, and the leaching of the activated nickel sulfide concentrate under the conditions that the leaching temperature is 60 ℃, 70 ℃, 80 ℃ and 90 ℃ is respectively inspected. Table 3 shows the effect of leaching temperature on leaching efficiency of activated nickel sulphide concentrate, and the experimental results obtained under the above conditions are shown in table 3.
Table 3: influence of leaching temperature on leaching efficiency of activated nickel sulfide concentrate
| Leaching temperature/. degree.C | Co | | Fe | Ni | |
| 60 | 80％ | 78％ | 65％ | 80％ | |
| 70 | 85％ | 85％ | 47％ | 85％ | |
| 80 | 93％ | 91％ | 39％ | 93％ | |
| 90 | 95.5％ | 92.35％ | 36.74％ | 97.05％ |
As can be seen from table 3, when the leaching temperature is increased from 60 ℃ to 90 ℃, the leaching rates of nickel, cobalt and copper are increased and the leaching rate of iron is decreased as the leaching temperature is increased, so that the leaching efficiency of nickel, cobalt and copper and the leaching efficiency of iron are considered together, the preferred range of the leaching temperature is 80 ℃ to 100 ℃, and the optimal leaching temperature is selected to be 90 ℃.
On the other hand, the mechanical stirring is adopted in the stirring mode in the experimental part, and compared with the magnetic stirring mode adopted in other experimental parts in the examples, under the same conditions, the leaching rates of nickel, cobalt and copper are improved, and the leaching rate of iron is greatly reduced, so the mechanical stirring mode is preferably adopted.
(7) Investigating the influence of leaching time on the preparation of nickel sulfide concentrate leachate
Wherein the reaction conditions are selected as follows: the ball milling strength is 10G, the ball-to-material ratio is 20:1, the ball milling time is 180min, the dosage of a sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/G, the introduction flow of oxygen is 0.8L/min, the mechanical stirring speed is 300rpm, the leaching temperature of the activated nickel sulfide concentrate is 90 ℃, the end-point pH value of the leaching process is 2.5, and the leaching of the activated nickel sulfide concentrate is respectively considered under the conditions that the leaching time is 60min, 120min, 180min, 240min, 300min and 360 min. Table 4 shows the effect of leaching time on leaching efficiency of activated nickel sulphide concentrate, and the experimental results obtained under the above conditions are shown in table 4.
Table 4: influence of leaching time on leaching efficiency of activated nickel sulfide concentrate
As can be seen from table 4, when the leaching time is increased from 60min to 300min, the leaching efficiency of cobalt is increased from 58% to 95.5%, the leaching efficiency of copper is increased from 74% to 92.35%, the leaching efficiency of nickel is increased from 70% to 97.05%, and the leaching efficiency of iron is decreased from 51% to 36.37%, and then the leaching time is increased from 300min to 360min, the leaching efficiency of nickel, cobalt, copper and iron has no significant change, therefore, in summary, the leaching time is preferably 240min to 360min, and the leaching time is optimally selected to be 300 min.
(8) Investigating the influence of oxygen flow on the preparation of nickel sulfide concentrate leachate
Wherein the reaction conditions are selected as follows: the ball milling strength is 10G, the ball-to-material ratio is 20:1, the ball milling time is 180min, the dosage of a sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/G, the mechanical stirring speed is 300rpm, the leaching temperature of the activated nickel sulfide concentrate is 90 ℃, the leaching time is 300min, the end-point pH value of the leaching process is 2.5, and the leaching of the activated nickel sulfide concentrate under the conditions that the introduction flow of oxygen is 0.4L/min, 0.8L/min and 1.0L/min is respectively considered. Table 5 shows the effect of oxygen flow on the leaching efficiency of the activated nickel sulphide concentrate, and the experimental results obtained under the above conditions are shown in table 5.
Table 5: influence of oxygen flow on leaching efficiency of activated nickel sulfide concentrate
| Oxygen flow (L/min) | Co | Cu | Fe | Ni |
| 0.4 | 73％ | 62％ | 49％ | 79％ |
| 0.8 | 95.5％ | 92.35％ | 36.74％ | 97.05％ |
| 1.0 | 96％ | 93％ | 33％ | 98％ |
As can be seen from Table 5, when the oxygen flow rate is increased from 0.4L/min to 0.8L/min, the leaching efficiency of cobalt is increased from 73% to 95.5%, the leaching efficiency of copper is increased from 62% to 92.35%, the leaching efficiency of nickel is increased from 79% to 97.05%, and the leaching efficiency of iron is decreased from 49% to 36.37%, and then the oxygen flow rate is increased from 0.8L/min to 1.0L/min, the leaching efficiency of nickel, cobalt, copper and iron has no significant change, therefore, in summary, the oxygen flow rate is preferably 0.6L/min to 1.0L/min, and the oxygen flow rate is optimally selected to be 0.8L/min.
In summary, the optimized process conditions for preparing the leaching solution of the nickel sulfide concentrate are as follows: the ball milling strength is 10G, the ball-to-material ratio is 20:1, the ball milling time is 180min, the dosage of a sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.30mL/G, the introduction flow of oxygen is 0.8L/min, the mechanical stirring speed is 300rpm, the leaching time of the activated nickel sulfide concentrate is 300min, the leaching temperature is 90 ℃, and the end-point pH value of the leaching process is 2.5.
And under the optimized process conditions, after the leaching reaction of the activated nickel sulfide concentrate is finished, filtering the activated nickel sulfide concentrate to obtain a nickel sulfide concentrate leachate, wherein the leaching rates of nickel, cobalt, copper and iron in the nickel sulfide concentrate are respectively 97.05%, 95.5%, 92.35% and 36.74%, and the metal elements in the nickel sulfide concentrate leachate at least comprise copper, iron, cobalt, nickel, magnesium and calcium elements.
Example 2: removing copper ions and iron ions in nickel sulfide concentrate leaching solution
Step one, adding hydrogen peroxide into the nickel sulfide concentrate leachate obtained under the optimized process conditions of the embodiment 1 to oxidize ferrous ions in the leachate into ferric ions to form a first solution.
Secondly, adding phosphate into the first solution to enable iron ions and copper ions in the first solution to respectively react to generate copper phosphate precipitates and iron phosphate precipitates, filtering after the reaction is finished to respectively obtain solid-phase copper phosphate slag and solid-phase iron phosphate slag, and obtaining a liquid-phase second solution, namely the leachate from which the copper ions and the iron ions are removed; wherein the excess coefficient of the usage amount of the phosphate is 1, the reaction temperature is 80 ℃, the reaction time is 120min, and the end point pH is controlled to be 2-3 in the reaction process, based on the usage amount of the iron ions and the copper ions in the first solution, which are completely precipitated.
(1) Under the above conditions, the influence of pH during the reaction of adding phosphate to generate iron phosphate precipitate on the removal of copper and iron ions from the nickel sulfide concentrate leachate was examined.
Fig. 8 is a graph showing the relationship between the pH during the reaction for adding phosphate to generate iron phosphate precipitate and the ion removal rate of each metal ion in the nickel sulfide concentrate leachate, and the experimental results obtained under the above conditions are shown in fig. 8.
As can be seen from fig. 8, when the end point pH was 1.5, the removal efficiency of iron and phosphorus was only 77%, but when the end point pH was increased to 2.5, the removal efficiency of iron and phosphorus in the solution reached more than 98.5%. Therefore, when the phosphate method is adopted for removing iron, the pH value in the reaction process of adding phosphate to generate iron phosphate precipitate is controlled to be 2.5 optimally.
In summary, the optimized process conditions for removing copper ions and iron ions in the leaching solution of the nickel sulfide concentrate are as follows: according to the using amount of completely precipitated iron ions and copper ions in the first solution as a reference, the excess coefficient of the using amount of the phosphate is 1, the reaction temperature is 80 ℃, the reaction time is 120min, and the end point pH value is controlled to be 2.5 in the reaction process. Under the optimized process conditions, after the reaction is finished, solid-liquid separation is carried out to obtain iron phosphate slag, copper phosphate slag sediment and nickel sulfide concentrate leachate without copper ions and iron ions.
The ICP composition characterization of the iron phosphate slag obtained above, the ICP main metal element composition characterization of the iron phosphate slag, and the leachate composition analysis results are shown in table 6.
Table 6: characterization (ICP) of main metal element components in iron phosphate slag and analysis of leachate components
As can be seen from Table 6, the iron phosphate slag contained Fe of 27.98% and Ni and Co of only 0.18% and 0.02%, indicating that the loss of Ni is 2% or less and that the loss of Co is almost zero; the concentration of iron ions in the nickel sulfide concentrate leachate obtained after iron removal is only 0.73g/L, and the content of phosphorus is 0.04g/L, which indicates that the residual phosphorus in the leachate can be controlled under the condition of ensuring iron removal by adopting the phosphate method for iron removal.
Fig. 9 is a phase characterization (XRD) of the iron phosphate slag, and the obtained iron phosphate slag has an amorphous structure, so that the iron phosphate slag needs to be dissolved and then recrystallized to prepare iron phosphate, thereby realizing resource utilization of the iron phosphate.
Example 3: removing calcium ions and magnesium ions in nickel sulfide concentrate leaching solution
Placing the second solution obtained under the optimized process conditions of the example 2, namely the leachate without iron ions and copper ions in a constant-temperature water bath kettle and stirring, adding a sodium carbonate solution to enable the second solution to reach a preset pH value, adding sodium fluoride serving as a precipitator into the second solution, carrying out precipitation reaction on magnesium ions and calcium ions in the second solution and the sodium fluoride, and carrying out solid-liquid separation after the reaction is finished to obtain a liquid-phase third solution, namely the leachate without calcium ions and magnesium ions.
(1) And (4) investigating the influence of the end-point pH value on the removal of calcium ions and magnesium ions in the nickel sulfide concentrate leachate.
Wherein the reaction conditions are selected as follows: the temperature of the constant-temperature water bath is 90 ℃, the mass fraction of the sodium carbonate solution is 7%, the reaction time is 1.5h, and the excess coefficient of the amount of the sodium fluoride is 1.5 on the basis of the amount of the magnesium ions and the calcium ions in the second solution which are completely precipitated; the removal rates of magnesium ions and calcium ions in the leachate were examined respectively at predetermined pH values, i.e., end point pH values of 4.0, 4.5, and 5.0. Fig. 10 is a graph showing the relationship between the end point pH and the removal rate of calcium ions and magnesium ions from the leachate of nickel sulfide concentrate, and the experimental results obtained under the above conditions are shown in fig. 10.
As can be seen from fig. 10, as the end point pH increased from 4.0 to 4.5, the removal efficiency of magnesium increased from 95.16% to 98.61%, and the removal efficiency of calcium increased from 75.61% to 97.3%, at which time the increase in the removal efficiency of magnesium was insignificant and the removal efficiency of calcium increased significantly; when the end point pH is increased from 4.5 to 5.0, the removal efficiency of magnesium is changed from 98.61% to 98.86%, basically no change is made, and the removal efficiency of calcium is reduced from 97.3% to 96.48%. In conclusion, the end point pH value is preferably 4-5, and when the end point pH value is 4.5, the effect of removing calcium ions and magnesium ions in the nickel sulfide concentrate leachate is the best.
(2) And investigating the influence of the reaction temperature on the removal of calcium ions and magnesium ions in the nickel sulfide concentrate leachate.
Wherein the reaction conditions are selected as follows: the mass fraction of the sodium carbonate solution is 7%, the end-point pH value is 4.5, and the reaction time is 1.5 h; according to the reference of the dosage of completely precipitating the magnesium ions and the calcium ions in the second solution, the excess coefficient of the dosage of the sodium fluoride is 1.5, and the removal rates of the magnesium ions and the calcium ions in the leachate are respectively considered under the conditions that the temperature of a constant-temperature water bath, namely the reaction temperature, is 70 ℃, 80 ℃ and 90 ℃. Fig. 11 is a graph showing the relationship between the reaction temperature and the removal rate of calcium ions and magnesium ions from the leachate of nickel sulfide concentrate, and the experimental results obtained under the above conditions are shown in fig. 11.
As can be seen from fig. 11, as the reaction temperature was increased from 70 ℃ to 90 ℃, the removal efficiency of magnesium was changed from 99.52% to 98.61%, and the removal rate of magnesium was not substantially changed; the calcium removal efficiency is increased from 92.95% to 97.3%, and the calcium removal efficiency is slightly increased, which shows that the reaction temperature has no influence on the calcium and magnesium removal efficiency. However, under high temperature conditions, calcium fluoride and magnesium fluoride generated in the process of precipitation reaction of sodium fluoride with magnesium ions and calcium ions are easy to form colloid, which causes problems of long filtration process time, difficult filtration, metal ion adsorption and the like, so the reaction temperature should not be controlled too high. In summary, the reaction temperature is preferably 70 ℃ to 100 ℃, and the reaction temperature is most preferably 90 ℃.
(3) And (3) investigating the influence of the excess coefficient of the using amount of the sodium fluoride on the removal of calcium ions and magnesium ions in the nickel sulfide concentrate leaching solution.
Wherein the reaction conditions are selected as follows: the temperature of the constant-temperature water bath kettle is 90 ℃, the mass fraction of the sodium carbonate solution is 7%, the reaction time is 1.5h, and the end-point pH value is 4.5; the removal rates of magnesium ions and calcium ions in the leachate were examined under the conditions of an excess coefficient of the amount of sodium fluoride of 1.0, 1.25, 1.5, 1.75 and 2.0, respectively. Fig. 12 is a graph showing the relationship between the excess factor of the amount of sodium fluoride and the removal rate of calcium ions and magnesium ions from the leachate of nickel sulfide concentrate, and the experimental results obtained under the above conditions are shown in fig. 12.
As can be seen from fig. 12, when the excess factor of the amount of sodium fluoride was increased from 1.0 to 1.5, the removal efficiencies of calcium and magnesium were increased from 79.5% and 84.6% to 97.3% and 98.6%, respectively. The removal efficiency of calcium and magnesium is not obviously increased by continuously increasing the dosage of sodium fluoride, and F in the solution can be caused-The ions are excessive and new impurities are generated. In summary, the excess factor of the amount of sodium fluoride is preferably 1.25 to 2.0, and the excess factor of the amount of sodium fluoride is preferably 1.5.
In summary, the optimized process conditions for removing copper ions and iron ions in the leaching solution of the nickel sulfide concentrate are as follows: the reaction temperature is 90 ℃, and the end-point pH value is 4.5; the excess factor of the amount of sodium fluoride was 1.5 based on the amount of magnesium ions and calcium ions in the second solution completely precipitated.
Example 4: extracting and separating cobalt ions in nickel sulfide concentrate leachate by an extraction process
Step one, preparing an extraction organic phase containing a P204 extraction agent, taking a third solution obtained under the optimized process conditions of the embodiment 3, namely the leachate without magnesium ions and calcium ions as an extraction water phase, removing impurities through an extraction process, and separating after extraction is finished to obtain a third solution after impurities are removed, namely the leachate without trace copper, iron and aluminum metal impurities.
Wherein the reaction conditions are selected as follows: the volume fraction of the P204 extractant in the extracted organic phase is 20%, and the saponification rate of the P204 extractant is 60%; the extraction ratio is 1:1, the extraction temperature is 25 ℃, the extraction time is 10min, the standing time is 10min, and the pH value in the reaction process is controlled to be 3.5.
Step two, performing extraction separation of cobalt ions by using the extraction organic phase containing the P507 extraction agent relative to the third solution after impurity removal: preparing an extraction organic phase containing a P507 extraction agent, taking the impurity-removed third solution as an extraction water phase, extracting and separating cobalt ions through an extraction process, and separating to obtain a loaded organic phase and a nickel-containing raffinate after extraction is finished, wherein the loaded organic phase is a cobalt-containing organic phase.
Wherein the reaction conditions are selected as follows: the volume fraction of the P507 extracting agent in the extracted organic phase is 25%, and the saponification rate of the P507 extracting agent in the extracted organic phase is 70%; the extraction ratio is 2:1, the extraction temperature is 25 ℃, the extraction time is 10min, the standing time is 10min, and the pH value in the reaction process is controlled to be 3.25.
Example 5: preparation of cobalt sulfate product
Step one, the loaded organic phase obtained in example 4 was washed with a sulfuric acid solution having a concentration of 0.2 mol/L.
And step two, back-extracting the washed loaded organic phase by using a sulfuric acid solution with the concentration of 2.0mol/L to obtain a cobalt sulfate solution.
Wherein the reaction conditions are selected as follows: the concentration of the sulfuric acid solution is 2mol/L, the time of back extraction is 20min, and the extraction phase ratio (O/A) is 2.5: 1.
and step three, heating, evaporating and concentrating the cobalt sulfate solution, and then cooling and crystallizing to obtain the cobalt sulfate product.
Wherein the reaction conditions are selected as follows: the heating temperature is 90 ℃, the cooling temperature is 58 ℃, and the crystallization time is 2 h.
Example 6: preparation of nickel sulfate product
Step one, adding sodium hydroxide solution into the nickel-containing raffinate obtained in the example 4, and after the reaction is finished, performing solid-liquid separation to obtain solid-phase nickel hydroxide precipitate.
Wherein the temperature of the reaction solution is controlled to be 90 ℃, the pH value of the reaction solution is controlled to be 9, the mass fraction of the sodium hydroxide solution is 10%, and the reaction time is 4 h.
And step two, dissolving the nickel hydroxide precipitate by using a sulfuric acid solution to obtain a nickel sulfate solution.
Wherein the reaction temperature is controlled to be 60 ℃, the pH value of the reaction solution is controlled to be 3.5-3.6, the reaction time is 4 hours, and the concentration of the nickel in the nickel sulfate solution is 100 g/L.
And step three, heating, evaporating and concentrating the nickel sulfate solution at 90 ℃ until the concentration of nickel is more than 300g/L, then cooling, crystallizing, controlling the temperature to be 53 ℃, controlling the pH value in the reaction process to be 3.5-3.6, and preparing the nickel sulfate product.
The nickel element in the nickel sulfide concentrate can be recycled by preparing the nickel sulfate product
According to the invention, the nickel sulfide concentrate is pretreated by mechanical activation, so that the reaction activity of the nickel sulfide concentrate is improved, and microbubbles are introduced to enhance oxidation to control leaching and precipitation behaviors of iron in the leaching process, so that the valuable metals of nickel, cobalt and copper in the nickel sulfide concentrate are efficiently leached under normal pressure, the leaching of iron is inhibited, and the leaching rates of nickel, cobalt, copper and iron in the nickel sulfide concentrate are respectively 97.1%, 95.5%, 92.4% and 36.7%. Then, iron ions in the leachate of the nickel sulfide ore can be removed efficiently by adopting phosphate for removing iron, the loss of nickel element and cobalt element is below 2%, and the influence of iron ions with higher concentration on the recovery process flow and energy consumption of nickel is solved. Finally, metal impurities in the nickel sulfide concentrate leachate are sequentially subjected to impurity removal, nickel elements are recycled by preparing a nickel sulfate product, and the separated main metal elements such as cobalt and the like can be further utilized, so that the resource utilization rate is improved. Therefore, the method not only realizes the efficient recycling of the nickel element and the cobalt element in the nickel sulfide concentrate, but also further utilizes other metal elements, is favorable for improving the utilization value of raw materials and reducing the pollution of the raw materials to the environment.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (8)
1. A process for selectively extracting cobalt and nickel from a nickel sulfide concentrate, the process comprising:
s10, placing the nickel sulfide concentrate into a ball mill for ball milling treatment, and performing mechanical activation treatment on the nickel sulfide concentrate to form activated nickel sulfide concentrate;
s20, placing the activated nickel sulfide concentrate into a leaching solution, introducing gas into the leaching solution to form micro bubbles, and stirring to leach metal elements in the activated nickel sulfide concentrate to obtain a nickel sulfide concentrate leachate, wherein the metal elements at least comprise copper, iron, cobalt, nickel, magnesium and calcium elements;
s30, removing iron by a phosphate method, comprising the following steps: adding an oxidant to the nickel sulphide concentrate leachate to oxidize ferrous ions in the leachate to ferric ions to form a first solution; adding phosphate into the first solution to enable iron ions and copper ions in the first solution to react respectively to generate precipitates, and performing solid-liquid separation to remove the precipitates to obtain a liquid-phase second solution;
wherein the oxidant is selected from any one of hydrogen peroxide, sodium chlorate, sodium hypochlorite, ammonium persulfate and sodium persulfate; adding phosphate to perform precipitation reaction, wherein the reaction temperature is 60-80 ℃, the reaction time is 30-120 min, and the end point pH is controlled to be 2-3 in the reaction process;
s40, adding sodium fluoride serving as a precipitating agent into the second solution to enable magnesium ions and calcium ions in the second solution to have a precipitation reaction, and after the reaction is finished, carrying out solid-liquid separation to obtain a liquid-phase third solution;
s50, preparing an extraction organic phase containing a P507 extraction agent, taking the third solution as an extraction water phase, extracting and separating cobalt ions through an extraction process, and separating to obtain a loaded organic phase and a nickel-containing raffinate after extraction is finished;
s60, carrying out back extraction on the loaded organic phase to obtain cobalt-containing back extraction liquid, and preparing a cobalt sulfate product by taking the cobalt-containing back extraction liquid as a raw material;
s70, preparing and obtaining a nickel sulfate product by taking the nickel-containing raffinate as a raw material.
2. The method as claimed in claim 1, wherein the process conditions of the ball milling treatment in the step S10 include: the ball milling strength is 7.5G-15G, the ball-material ratio is 15: 1-30: 1, and the ball milling time is 120 min-240 min; the particle size range of the activated nickel sulfide concentrate after ball milling is that D50 is less than or equal to 15 mu m.
3. The method according to claim 1, wherein in the step S20, the leaching solution is a sulfuric acid solution, the dosage of the sulfuric acid solution relative to the activated nickel sulfide concentrate is 0.20mL/g to 0.40mL/g, the gas introduced into the leaching solution is oxygen, the introduction flow rate of the oxygen is 0.6L/min to 1.0L/min, the leaching time of the activated nickel sulfide concentrate is 240min to 360min, the leaching temperature is 80 ℃ to 100 ℃, and the end-point pH in the leaching process is 1 to 3.
4. The method according to claim 1, wherein the step S40 specifically includes: and (2) placing the second solution in a constant-temperature water bath, stirring, adding a sodium carbonate solution to enable the second solution to reach a preset pH value, adding sodium fluoride serving as a precipitating agent into the second solution, carrying out precipitation reaction on magnesium ions and calcium ions in the second solution and the sodium fluoride, and carrying out solid-liquid separation after the reaction is finished to obtain a liquid-phase third solution.
5. The method according to claim 4, wherein in the step S40, the temperature of the constant temperature water bath is 70-100 ℃, and the predetermined pH value is 4-5; and the excess coefficient of the amount of the sodium fluoride is 1.25-2.0 based on the amount of the magnesium ions and the calcium ions in the second solution which are completely precipitated.
6. The method according to claim 1, wherein in step S50,
firstly, preparing an extraction organic phase containing a P204 extraction agent, taking the third solution as an extraction water phase, removing impurities through an extraction process, and separating after extraction to obtain a third solution after impurity removal;
then, the extraction organic phase containing the P507 extraction agent is used for carrying out extraction separation on cobalt ions on the third solution after impurity removal.
7. The method according to claim 1, wherein the step S60 specifically includes:
washing the loaded organic phase by using a sulfuric acid solution with the concentration of 0.1-0.4 mol/L;
carrying out back extraction on the washed loaded organic phase by using a sulfuric acid solution with the concentration of 1.0-2.0 mol/L to obtain a cobalt sulfate solution;
and heating, evaporating and concentrating the cobalt sulfate solution, and then cooling and crystallizing to obtain the cobalt sulfate product.
8. The method according to claim 1, wherein the step S70 specifically includes:
adding a sodium hydroxide solution into the nickel-containing raffinate, controlling the temperature of the reaction solution to be 80-100 ℃, controlling the pH value of the reaction solution to be 9-10, and performing solid-liquid separation after the reaction to obtain solid-phase nickel hydroxide precipitate;
dissolving the nickel hydroxide precipitate by using a sulfuric acid solution to obtain a nickel sulfate solution; controlling the reaction temperature to be 50-80 ℃, controlling the pH value of the reaction solution to be 3-4, and obtaining the nickel concentration in the nickel sulfate solution to be 80-100 g/L;
and (3) heating, evaporating and concentrating the nickel sulfate solution at 90-100 ℃ until the concentration of nickel is more than 300g/L, and then cooling, cooling and crystallizing to obtain a nickel sulfate product.
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| CN114737066A (en) * | 2022-04-20 | 2022-07-12 | 北京中科云腾科技有限公司 | Method for extracting lithium from lithium ore leaching slag |
| CN115611260A (en) * | 2022-12-15 | 2023-01-17 | 中国科学院过程工程研究所 | Method for extracting micro-bubble reinforced phosphate rock acidolysis solution |
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| CN115611260A (en) * | 2022-12-15 | 2023-01-17 | 中国科学院过程工程研究所 | Method for extracting micro-bubble reinforced phosphate rock acidolysis solution |
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