CN116377218A - Method and system for comprehensively utilizing high-magnesium nickel sulfide ore by low-temperature oxygen enrichment method - Google Patents
Method and system for comprehensively utilizing high-magnesium nickel sulfide ore by low-temperature oxygen enrichment method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 157
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 102
- 239000001301 oxygen Substances 0.000 title claims abstract description 102
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002386 leaching Methods 0.000 claims abstract description 230
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 155
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011777 magnesium Substances 0.000 claims abstract description 90
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 78
- 239000002893 slag Substances 0.000 claims abstract description 65
- 230000008569 process Effects 0.000 claims abstract description 52
- 238000002791 soaking Methods 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 150000002739 metals Chemical class 0.000 claims abstract description 22
- 239000012141 concentrate Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 157
- 229910052742 iron Inorganic materials 0.000 claims description 73
- 239000007788 liquid Substances 0.000 claims description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- 238000000498 ball milling Methods 0.000 claims description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 49
- 229910052802 copper Inorganic materials 0.000 claims description 49
- 239000010949 copper Substances 0.000 claims description 49
- 239000007787 solid Substances 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 32
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 30
- 229910052598 goethite Inorganic materials 0.000 claims description 26
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- 229910017052 cobalt Inorganic materials 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 25
- 238000000605 extraction Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 15
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 230000001698 pyrogenic effect Effects 0.000 claims description 15
- 238000004137 mechanical activation Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 13
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000001238 wet grinding Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- 230000001276 controlling effect Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000005188 flotation Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 31
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 19
- 239000012535 impurity Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- -1 nickel Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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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
- C22B23/04—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
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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Abstract
The invention discloses a method and a system for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen-enriched method. The method comprises the following steps: taking high-magnesium nickel sulfide ore as a raw material for pre-soaking and removing magnesium to obtain pre-soaking slag; mechanically activating the presoaked slag to obtain activated ore pulp; and leaching the activated ore pulp by adopting low-temperature oxygen-enriched leaching to obtain a nickel-containing leaching solution. The invention has the advantages of wide application range, simplicity, reliability, easy control of the process and low investment cost, and can convert metals into corresponding products, thereby realizing the treatment of the high-magnesium nickel sulfide concentrate with low cost and high benefit.
Description
Technical Field
The invention relates to the technical field of nickel sulfide ore treatment processes, in particular to a method and a system for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen-enriched method.
Background
The nickel sulfide ore has the characteristics of complex components, low grade, more associated gangue, refractory materials and the like, so that the treatment process for the nickel sulfide ore is complex. The existing production process mainly comprises two kinds of processes:
first, a combined process of a fire method and a wet method. Firstly, smelting and converting nickel sulfide ore by a pyrogenic process, and enriching valuable metals into nickel matte; and then separating and refining nickel, copper and cobalt in the high-nickel matte. The combined process has the defects of long flow, low metal direct yield, high investment cost and the like. Additionally, and of particular importance, the inventors herein have found that: when the high-magnesium nickel sulfide ore is treated by the combined process, the ore needs to be further subjected to magnesium reduction treatment to carry out pyrometallurgy, so that the high-magnesium nickel sulfide ore cannot be directly treated by the combined process.
And secondly, a wet direct leaching process. Carrying out multistage normal pressure and pressure leaching by utilizing the difference of reaction behaviors of various substances in nickel sulfide ore under different conditions in sulfuric acid solution, wherein nickel, cobalt, magnesium and the like enter leaching liquid, and iron, sulfur and the like enter leaching slag; the leachate is subjected to impurity removal, extraction, refining and the like to obtain refined products of each metal. Compared with the combined fire and wet process, the wet process has the advantages of short flow, low investment cost and the like. However, the present inventors have studied to find that: the wet process still has the following problems: (1) no pre-removal of magnesium from the feedstock prior to leaching. When treating high-magnesium nickel sulfide ore, magnesium completely enters the leaching solution in the leaching process and enters the extraction process as impurity ions, so that the extraction stage number is increased, and the operation difficulty is increased. (2) The raw materials are directly leached without being activated, the leaching is required to be carried out under high acid, high temperature and high pressure, the requirements on the operation and equipment materials are high, the energy consumption is high, and the scaling phenomenon is caused in the leaching process due to high magnesium. (3) The high-magnesium nickel sulfide concentrate has higher sulfur content, is leached by a high-temperature one-step method, and most of sulfur elements are oxidized into sulfuric acid, so that the balance of heat, sulfuric acid and sulfur elements is difficult to realize, and a large amount of neutralizers are needed. Meanwhile, most of impurity ions are leached out, and the subsequent impurity removal pressure is high.
Based on the findings, the inventor obtains the process for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method through further research.
Disclosure of Invention
According to one embodiment of the invention, the method and the system for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen-enriched method are provided. The above object can be achieved by the following embodiments of the present invention:
according to one aspect of the invention, the method for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method provided by the invention comprises the following steps: taking high-magnesium nickel sulfide ore as a raw material, pre-soaking for removing magnesium to obtain magnesium-containing pre-soaking liquid and pre-soaking slag; mechanically activating the presoaked slag by adopting a ball milling method to obtain activated ore pulp; leaching the activated ore pulp by adopting a low-temperature oxygen-enriched method to obtain a leaching solution containing nickel and leaching residues; and (3) carrying out post-treatment by adopting the nickel-containing leaching solution, and converting metals in the nickel-containing leaching solution into corresponding products.
Optionally, when the magnesium is pre-soaked and removed, sulfuric acid is used as a leaching reagent, and the concentration of the sulfuric acid is 60 g/L-100 g/L; the mechanical activation is carried out by adopting a wet ball milling mode, wherein the ball-material ratio is 5:1-35:1, the ball milling strength is 5G-25G, and the reaction temperature is controlled to be 100-140 ℃ during leaching by a low-temperature oxygen-enriched method.
Optionally, when pre-soaking and removing magnesium, sulfuric acid is used as a leaching reagent, and liquid-solid separation is carried out after leaching for 0.5-3 h at normal temperature by stirring; wherein the concentration of sulfuric acid is 80 g/L-100 g/L; the addition amount of sulfuric acid is determined according to the magnesium oxide content of the high-magnesium nickel sulfide ore, and the liquid-solid ratio is controlled to be 2:1-5:1.
Optionally, after pre-soaking and magnesium removing, the leaching rate of magnesium oxide is more than or equal to 90%, the leaching rates of nickel, cobalt and copper in magnesium-containing pre-leaching liquid are all less than 5%, and the leaching rate of iron is less than 7%.
Optionally, during mechanical activation, wet ball milling is adopted, wherein the ball-material ratio is 5:1-35:1, the ball milling strength is 5G-25G, and the ball milling time is 0.5 h-5 h. Preferably, the ball-material ratio is 25:1-35:1, and the ball milling strength is 15G-25G.
Optionally, when leaching by a low-temperature oxygen-enriched method, introducing oxygen or oxygen enriched as a leaching oxidant, controlling the reaction temperature to be 100-130 ℃, controlling the reaction pressure to be 0.3-1.0 MPa, and performing liquid-solid separation after stirring and oxygen enriched leaching for 0.5-5 h, wherein the liquid-solid ratio is 3:1-6:1.
Optionally, leaching by a low-temperature oxygen-enriched method to obtain a nickel-containing leaching solution, wherein the leaching rate of nickel is more than or equal to 95%, the leaching rate of cobalt is more than or equal to 95%, the leaching rate of copper is more than or equal to 90%, and the leaching rate of iron is less than 40%.
Optionally, in the high-magnesium nickel sulfide ore, the nickel content is 5% -15%, and the magnesium oxide content is 6% -20%.
Optionally, the post-treatment of the nickel-containing leaching solution comprises: and (5) copper removal, iron removal and nickel cobalt extraction are sequentially carried out.
Optionally, during decoppering, the nickel-containing leaching solution is decoppered by adopting an iron powder replacement method to obtain sponge copper and decoppered solution; the addition amount of the iron powder is 1-3 times of the theoretical amount of copper, and the reaction time is 0.5-2 h after stirring at normal temperature.
Optionally, during iron removal, the copper-removed liquid is subjected to iron removal by adopting a goethite method, so that iron-removed liquid and iron slag are obtained; wherein, adopt goethite method to remove copper back liquid deironing, include: regulating the pH value of the solution after copper removal to 3-4, wherein nickel carbonate is adopted as a pH regulator; introducing oxygen or oxygen-enriched air as iron-removing oxidant, controlling reaction temperature at 70-90 deg.C, stirring, reacting for 2-10 hr, and then liquid-solid separation.
Optionally, extracting the deironing liquid to obtain magnesium sulfate, cobalt sulfate products and nickel sulfate products, and sending the magnesium sulfate into evaporation crystallization; wherein, during extraction, P204 is adopted to extract nickel, and P507 is adopted to extract cobalt.
Optionally, the method further comprises: and (3) carrying out nickel precipitation on the deironing solution by adopting sodium carbonate to generate nickel carbonate and sodium sulfate, and sending the nickel carbonate serving as a pH regulator of the goethite method into the deironing step.
Optionally, the method further comprises: neutralizing the magnesium-containing pre-leaching solution by using a neutralizing agent, carrying out solid-liquid separation, evaporating and crystallizing to obtain a magnesium sulfate product, and sending the neutralized slag obtained by neutralization into a leaching step by a low-temperature oxygen-enriched method; wherein the neutralizer is one or two of magnesium oxide and magnesium carbonate.
Optionally, the method further comprises: and (3) floating the leached slag to obtain sulfur concentrate and tailings.
Optionally, the method further comprises: and treating tailings and iron slag after iron removal by a pyrogenic process to obtain an iron ore product, and sending the generated sulfur dioxide flue gas to be used as a leaching reagent for pre-soaking and removing magnesium after acid production.
According to another aspect of the invention, the system for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method provided by the invention comprises the following components:
the pre-soaking magnesium removing device is used for pre-soaking magnesium removing by taking high-magnesium nickel sulfide ore as a raw material to obtain magnesium-containing pre-soaking liquid and pre-soaking slag;
the mechanical activation device comprises a ball mill and is used for mechanically activating the presoaked slag obtained by the presoaking and demagging device to obtain activated ore pulp;
the low-temperature oxygen-enriched leaching device is used for leaching the activated ore pulp by adopting a low-temperature oxygen-enriched method to obtain a nickel-containing leaching solution and leaching slag;
the post-treatment device is used for carrying out post-treatment on the nickel-containing leaching solution and converting each metal into a corresponding product.
Optionally, the pre-soaking magnesium removing device comprises a tank body, a stirrer and a first filtering device, sulfuric acid is added into the tank body as a leaching reagent, the concentration of the sulfuric acid is 60 g/L-100 g/L, and when the pre-soaking magnesium removing device is used for pre-soaking, the liquid-solid ratio is 2:1-5:1, and the leaching is carried out under stirring for 0.5 h-3 h at normal temperature.
Optionally, the ball mill of the mechanical activation device adopts a wet milling mode, the ball-material ratio is 5:1-35:1, the ball milling strength is 5G-25G, and the ball milling time is 0.5 h-5 h.
Optionally, the low-temperature oxygen-enriched leaching device comprises a vertical autoclave and a second filtering device, wherein the vertical autoclave is provided with a leaching oxidant inlet, the temperature in the autoclave is 100-130 ℃, the pressure is 0.3-1.0 MPa, the liquid-solid ratio is 3:1-6:1 during leaching, and the stirring oxygen-enriched leaching is carried out for 0.5-5 h.
Optionally, the post-treatment device for the nickel-containing leaching solution comprises: the copper removal unit, the goethite iron removal unit, the third filtering device and the extraction unit are sequentially arranged; the decoppering unit is used for decoppering the nickel-containing leaching solution by adopting an iron powder replacement method to obtain sponge copper and decoppered liquid; the goethite iron removal unit is used for removing iron from the copper-removed liquid by adopting a goethite method, and filtering the copper-removed liquid by the filtering unit to obtain iron-removed liquid and iron slag; the extraction unit adopts P204 to extract nickel and P507 to extract cobalt, so as to obtain a nickel cobalt product;
optionally, the post-treatment device for nickel-containing leaching solution further comprises: and the nickel depositing device is respectively connected with the filtering unit and the goethite iron removing unit and is used for depositing nickel to the iron-removed liquid by adopting sodium carbonate to generate nickel carbonate and sodium sulfate, and sending the nickel carbonate into the goethite iron removing unit to be used as a goethite method pH regulator.
Optionally, the system further comprises: the magnesium-containing pre-leaching liquid treatment device is connected with the first filtering device and comprises a neutralization unit, a fourth filtering device and an evaporative crystallization unit which are sequentially arranged, wherein the fourth filtering device is also connected with the low-temperature oxygen-enriched leaching device and is used for conveying neutralization slag obtained by the neutralization unit into the low-temperature oxygen-enriched leaching device for treatment.
Optionally, the system further comprises: and the flotation unit is connected with the second filtering device and is used for carrying out flotation on the leached slag after separation to obtain sulfur concentrate and tailings.
Optionally, the system further comprises: the pyrogenic process treatment unit is respectively connected with the flotation unit and the third filtering device and is used for carrying out pyrogenic process treatment on tailings and iron-removed iron slag to obtain iron ore products; the pyrogenic process unit is also connected with an acid making device which is connected with a pre-soaking magnesium removing device and is used for sending sulfur dioxide flue gas generated in the pyrogenic process to the pre-soaking magnesium removing device for use as a leaching reagent after making acid.
The beneficial effects are that: according to one embodiment of the invention, a nickel sulfide concentrate with high magnesium content is used as a raw material, firstly pre-soaked for magnesium removal, then mechanically activated and leached by a low-temperature oxygen-enriched method based on activated ore pulp to obtain a nickel-containing leaching solution, and the nickel-containing leaching solution is used for post-treatment, such as decoppering, iron removal, extraction and the like, to obtain a refined product of each metal. The method has low requirements on raw materials, wide process application range and capability of treating nickel sulfide ores with high magnesium content; the treatment method is simple and reliable, and the process is easy to control; the investment cost is low, the process flow is short, and the low-cost and high-benefit treatment of the high-magnesium nickel sulfide concentrate is realized; the implementation mode is flexible, has small restriction on the product scheme, and can realize wide market demands.
In addition, in the alternative scheme, intermediate products such as magnesium sulfate, sulfur concentrate, sponge copper, iron ore and the like can be prepared from magnesium removal liquid, leaching slag, copper slag, iron slag and the like, so that all metals are converted into corresponding products, the full comprehensive utilization of the high-magnesium nickel sulfide ore is realized, high economic benefit is brought, and the metal recovery rate is high.
Drawings
FIG. 1 is a process flow diagram of a method for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen enrichment method in an embodiment of the invention.
FIG. 2 is a schematic diagram of a connection structure of a system for comprehensively utilizing high-magnesium nickel sulfide ores by a low-temperature oxygen enrichment method in an embodiment of the invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
FIG. 2 schematically illustrates a connection structure of a system for comprehensively utilizing high-magnesium nickel sulfide ores by a low-temperature oxygen enrichment method in an embodiment of the present invention. As shown in fig. 2, the system comprises a pre-soaking magnesium removing device, a mechanical activating device, a low-temperature oxygen-enriched leaching device and a post-treatment device for the leaching liquid containing nickel. When the system is adopted to comprehensively utilize the high-magnesium nickel sulfide ore by a low-temperature oxygen-enriched method, the high-magnesium nickel sulfide ore is taken as a raw material, firstly, the magnesium is pre-soaked and removed, and then the leaching solution containing nickel is obtained by mechanical activation and leaching by the low-temperature oxygen-enriched method; converting the metal in the nickel-containing leaching solution into corresponding products by adopting post-treatment processes such as copper removal, iron removal, extraction and the like; the method has the advantages of low requirement on raw materials, wide application range, good applicability on the high-magnesium nickel sulfide ore, simplicity, reliability, easy control of the process, low investment cost and the like, and realizes the low-cost and high-benefit treatment of the high-magnesium nickel sulfide ore.
In addition, as shown in fig. 2, the system can also comprise a magnesium-containing pre-leaching liquid treatment device, a flotation unit and a pyrogenic treatment unit, which are used for preparing intermediate products such as magnesium removal liquid, leaching slag, copper slag, iron slag and the like into products such as magnesium sulfate, sulfur concentrate, sponge copper, iron ore and the like, so that all metals are converted into corresponding products, and the economic benefit is further improved.
FIG. 1 schematically shows a process flow diagram of a method for comprehensively utilizing high-magnesium nickel sulfide ores by a low-temperature oxygen-enriched method in an embodiment of the invention. As shown in fig. 1, this embodiment specifically includes the following steps:
and S10, pre-soaking and removing magnesium by taking high-magnesium nickel sulfide concentrate as a raw material, and performing solid-liquid separation to obtain magnesium-containing pre-soaking liquid and pre-soaking slag. The pre-soaking magnesium removing device comprises a tank body, a stirrer and a first filtering device. The raw material high-magnesium nickel sulfide concentrate is sulfide ore, the nickel content in the ore is 5% -15%, the magnesium oxide content is 6% -20%, such as 6%, 10%, 15%, 18%, 20%, and the like, and other metal types can contain one or more of copper, iron, zinc, cobalt and rare noble metals, and are not limited to the listed items. The method has low requirements on raw materials, wide application range and good applicability to high-magnesium nickel sulfide ores.
By pre-leaching the nickel sulfide ore, magnesium is separated before oxygen-enriched leaching, so that the problem that subsequent extraction is difficult to carry out due to a large amount of magnesium entering a process system is avoided, and the method has good applicability to the nickel sulfide ore with high magnesium content, which is difficult to treat in the current process. Meanwhile, the consumption of neutralizing agent in the subsequent magnesium-containing pre-immersion liquid treatment is relatively low, and the process impurity removal pressure is reduced.
In addition, in the preferred embodiment, when the pre-leaching magnesium removal is carried out, sulfuric acid is adopted as a leaching reagent, the concentration of the sulfuric acid is 60 g/L-100 g/L, preferably 80 g/L-100 g/L, the sulfuric acid is added according to the magnesium oxide content of the high-magnesium nickel sulfide ore, the liquid-solid ratio is 2:1-5:1, the stirring is carried out at normal temperature, the leaching is carried out for 0.5 h-3 h, and the liquid-solid separation is carried out by adopting a first filtering device, so that the pre-leaching liquid and the pre-leaching slag with magnesium as main components are obtained.
The concentration sulfuric acid is used as a leaching reagent for pre-soaking and magnesium removal, and meanwhile, the liquid-solid ratio and the leaching time are optimized, so that the leaching rate of magnesium oxide is improved, further, the magnesium is effectively prevented from entering a subsequent process, and the subsequent impurity removal pressure is also reduced; when the sulfuric acid with preferable concentration (80 g/L-100 g/L) is adopted for pre-leaching magnesium removal, the leaching rate of magnesium oxide is more than or equal to 90%, the leaching rate of nickel is less than 5%, the leaching rate of cobalt is less than 5%, the leaching rate of copper is less than 5%, and the leaching rate of iron is less than 7%.
In an alternative embodiment, a magnesium-containing pre-immersion liquid treatment device is adopted to neutralize the magnesium-containing pre-immersion liquid, solid-liquid separation and evaporation crystallization are carried out, and a magnesium sulfate product is obtained. The magnesium-containing pre-immersion liquid treatment device is connected with the first filtering device and comprises a neutralization unit, a fourth filtering device and an evaporation crystallization unit which are sequentially arranged; wherein, the fourth filtering device is also connected with the low-temperature oxygen-enriched leaching device. The pre-acidification liquid is magnesium-containing pre-impregnation liquid for neutralization, wherein the neutralizing agent adopts magnesium oxide, magnesium carbonate or a combination of the magnesium oxide and the magnesium carbonate, and no new impurity is added to the system. The method can adopt one-step impurity removal or multi-step impurity removal, solution concentration and other treatment steps according to the impurity types and the final production requirements of magnesium salt.
Illustratively, the treatment of the magnesium-containing pre-dip may comprise the steps of: 1) Adding a neutralizing agent into the magnesium-containing presoaked liquid for neutralization, and filtering by a fourth filtering device to obtain a magnesium sulfate solution and filter residues, namely neutralization residues. Wherein, the neutralizing agent adopts magnesium oxide. 2) And (3) evaporating and crystallizing the magnesium sulfate solution in an evaporating and crystallizing unit to obtain a magnesium sulfate product, and adding the neutralized slag into an oxygen-enriched leaching procedure. The neutralization slag generated in the neutralization process is mainly hydroxide of nickel, cobalt, copper, iron and the like, and the neutralization slag is added into the oxygen-enriched leaching process, so that the loss of valuable metals is avoided, and the metal recovery rate is further improved.
And S20, mechanically activating the presoaked slag by adopting a ball milling method to obtain activated ore pulp. The mechanical force is used for changing the material property, improving the ore leaching performance, creating conditions for the subsequent selective leaching, and enabling the leaching to be carried out under mild conditions, namely oxygen-enriched leaching under low temperature conditions.
In addition, in the preferred embodiment, the mechanical activation is performed by adopting a wet ball milling mode, wherein the ball-material ratio is 5:1-35:1, the ball milling strength is 5G-25G, and the ball milling time is 0.5 h-5 h.
The wet ball milling is adopted to activate the presoaked slag after presoaked magnesium removal, and the ball material ratio, the ball milling intensity and the ball milling time are controlled, so that the ore leaching performance can be further improved, the oxygen-enriched leaching can be carried out at the low temperature of not higher than 140 ℃, and the leaching rate is higher.
And S30, leaching the activated ore pulp by adopting a low-temperature oxygen-enriched method, and carrying out solid-liquid separation to obtain a nickel-containing leaching solution and leaching slag. The low-temperature oxygen-enriched leaching device is adopted, and comprises a vertical autoclave and a second filtering device, wherein the vertical autoclave is provided with a leaching oxidant through inlet.
The activated ore pulp obtained based on the ball milling activation step can be selectively leached under the relatively low temperature condition, so that nickel, cobalt, copper and the like enter leaching liquid, iron and sulfur remain in leaching slag, and a valuable metal-containing solution (namely nickel-containing leaching liquid) which can be easily treated is obtained, and the pressure of subsequent treatment is reduced. Not only can ensure the leaching rate of valuable metals, but also can realize the recycling of sulfur elements, inhibit sulfation, reduce the use of neutralizing agents, and has small subsequent treatment pressure.
In addition, in the preferred embodiment, when leaching is carried out by a low-temperature oxygen-enriched method, oxygen or oxygen enriched is introduced as a leaching oxidant, the reaction temperature is controlled to be 100-140 ℃, more preferably 100-130 ℃, the reaction pressure is 0.3-1.0 MPa, the liquid-solid ratio is 3:1-6:1, stirring is carried out, the oxygen enriched leaching is carried out for 0.5-5 h, and liquid-solid separation is carried out, thus obtaining leaching liquid and leaching slag.
The leaching rate of nickel, cobalt and copper is greatly improved by adopting a low-temperature oxygen-enriched method to leach ore pulp after ball milling activation and controlling the temperature, pressure, liquid-solid ratio and leaching time during leaching. The oxygen-enriched leaching temperature is controlled to be 100-130 ℃ in the reaction temperature, so that the iron content in the leaching solution can be further reduced; wherein, the leaching rate of nickel is more than or equal to 95%, the leaching rate of cobalt is more than or equal to 95%, the leaching rate of copper is more than or equal to 90%, and the leaching rate of iron is less than 40%.
And step S40, carrying out post-treatment on the nickel-containing leaching solution, and converting metals in the nickel-containing leaching solution into corresponding products. The nickel-containing leaching solution obtained in the steps S10 to S30 is an easily treated valuable metal-containing solution, and is subjected to post-treatment based on the nickel-containing leaching solution, so that the post-treatment pressure is reduced, and the leaching rate of the valuable metals is ensured.
In an alternative embodiment, a post-treatment device for the nickel-containing leaching solution is adopted to carry out post-treatment on the nickel-containing leaching solution, the device comprises a decoppering unit, a goethite deironing unit, a third filtering device and an extraction unit which are sequentially arranged, the decoppering unit is used for replacing decoppering by iron powder, the goethite deironing unit is used for removing iron by a goethite method, the extraction unit is used for extracting nickel and cobalt, wherein the iron powder replacement decoppering, the goethite deironing, the nickel and cobalt extraction and the like are all mature processes, and the conventional treatment method in the field is adopted. For example, the post-treatment may specifically include the following steps:
and S41, replacing and decoppering the nickel-containing leaching solution. Further, the nickel-containing leaching solution is decoppered by adopting an iron powder replacement method to obtain crude sponge copper and decoppered solution. Wherein, the addition amount of the iron powder is 1-3 times of the theoretical amount of copper, stirring is carried out at normal temperature, the reaction time is 0.5-2 h, and the liquid and the crude sponge copper after copper removal are obtained through solid-liquid separation. The copper recovery rate is improved by adopting displacement decoppering for the leaching solution containing nickel and simultaneously controlling the addition amount and time of iron powder; wherein the replacement recovery rate of copper is more than or equal to 99 percent, and the copper content in the obtained crude sponge copper is more than or equal to 40 percent.
And S42, deironing the copper-removed liquid by adopting a goethite method. Further, the method for removing iron from the copper-removed liquid by adopting goethite method comprises the following steps: regulating the pH value of the solution after copper removal to 3-4, wherein nickel carbonate is adopted as a pH regulator; introducing oxygen or oxygen-enriched air as an iron-removing oxidant, controlling the reaction temperature to be 70-90 ℃, stirring, reacting for 2-10 h, and separating liquid from solid to obtain iron-removed liquid and iron slag. Wherein, the iron content of the iron slag is more than or equal to 55 percent. The goethite method is adopted to remove iron from the copper-removed liquid, meanwhile, the pH value of the liquid is optimized, the reaction temperature and the reaction time are controlled, the iron removal rate is improved, the nickel-iron loss rate is reduced, most of nickel-cobalt valuable metals enter the iron-removed liquid, and the recovery rate of the subsequent nickel-cobalt valuable metals is further ensured; wherein the iron slag amount is about 0.55t/m 3 The removal rate of iron is more than or equal to 99 percent, the loss rate of nickel is less than 3 percent, and the loss rate of cobalt is less than 3 percent; in the deironing liquid, the nickel is 15 g/L-25 g/L, the cobalt is 0.2 g/L-1.5 g/L, and the iron is less than 0.02g/L.
And step S43, extracting the deironing liquid to obtain cobalt sulfate and nickel sulfate products. Wherein, during extraction, P204 is adopted to extract nickel, and P507 is adopted to extract cobalt, so that the extraction rate of nickel and cobalt can be improved.
In addition, the magnesium sulfate obtained after extraction is sent to an evaporation crystallization unit of a magnesium-containing pre-immersion liquid treatment device for evaporation crystallization, and a magnesium sulfate product is obtained.
In addition, a nickel precipitation device is adopted, sodium carbonate can be adopted for nickel precipitation of the iron-removed liquid, nickel carbonate and sodium sulfate are generated, and the nickel carbonate is used as a pH regulator of the goethite method to be sent to an iron removal step for use, so that comprehensive utilization is further realized, and cost is reduced. Both sodium sulfate and extracted sodium sulfate can be sold as products.
In an alternative embodiment, the leaching residue produced in step S30 is subjected to flotation using a flotation unit, and a sulphur concentrate product is obtained for sale while tailings are produced. The sulfur content of the sulfur concentrate product obtained by floatation of the leached slag is more than or equal to 50 percent.
Further, a pyrogenic process unit is adopted, the tailings are mixed with the iron slag obtained in the step S42, and solvent, natural gas and the like are added for pyrogenic smelting, so that an iron ore product is obtained; meanwhile, sulfur dioxide flue gas generated in the pyrogenic process is sent to an acid making unit for acid making treatment and then is sent to a pre-soaking magnesium removing process for use as a leaching reagent.
In addition, when the present application performs solid-liquid separation, the separation method includes: the method is not limited to the mentioned liquid-solid separation method, and may be any one of the following methods. The equipment used, i.e., the filtration apparatus, includes a thickener, a plate and frame filter press, a vertical filter press, a settling tank, a centrifuge, an adsorption column, a cyclone, and is not limited to the mentioned separation equipment.
In some embodiments described above, a nickel sulfide concentrate with high magnesium content is used as a raw material, and is first pre-soaked to remove magnesium, and then mechanically activated and leached by a low-temperature oxygen-enriched method to obtain a leaching solution containing valuable metals, i.e., nickel, which can be easily treated. Based on the nickel-containing leaching solution, refined products of various metals can be obtained through copper removal, iron removal, extraction and the like. And the intermediate product contains magnesium pre-leaching liquid, leaching slag, copper slag, iron slag and the like to prepare products such as magnesium sulfate, sulfur concentrate, sponge copper, iron ore and the like. The process has the advantages of wide application range, simplicity, reliability, easy control of the process and low investment cost, converts all metals into corresponding products, and realizes the treatment of the high-magnesium nickel sulfide concentrate with low cost and high benefit.
In some of the embodiments described above, the following advantages and benefits are also provided:
(1) Before selective leaching, the magnesium in the raw materials is subjected to presoaked separation, so that magnesium elements are reduced to enter a subsequent leaching process, the subsequent treatment load is reduced, and meanwhile, the production process of magnesium as a product is shortened. Particularly has good practicability for nickel sulfide ores with high magnesium content, such as not less than 6 percent.
(2) The mechanical activation process is adopted to treat the materials, so that the properties of the materials are changed, and a guarantee is provided for realizing low-temperature oxygen-enriched leaching; further, the wet ball milling process is adopted for activation, so that the oxygen-enriched leaching efficiency is further improved.
(3) The high-magnesium nickel sulfide concentrate has higher sulfur content, is leached by a high-temperature one-step method, is difficult to realize the balance of heat, sulfuric acid and sulfur elements, and realizes low-temperature leaching after mechanical activation, so that the leaching rate of valuable metals is ensured, the recycling of sulfur elements is realized, sulfation is inhibited, and the use of neutralizers is reduced.
(4) The invention obtains a valuable metal-containing solution which can be easily treated on the basis of the former process, so as to lighten the pressure of the subsequent treatment, and simultaneously adopts the process with lower cost and shorter process flow to prepare the product which can produce economic benefit.
(5) The nickel-containing leaching solution obtained based on the pre-soaking magnesium removal, mechanical activation and low-temperature oxygen-enriched leaching can be subjected to copper removal, iron removal and extraction in sequence to obtain products such as crude sponge copper, nickel sulfate, cobalt sulfate, iron ore and the like, the process is simple, the recovery rate of each metal is high, and the economic benefit is high.
(6) On the basis of pre-soaking and magnesium removal, mechanical activation and low-temperature oxygen-enriched leaching, the method combines magnesium-containing pre-soaking liquid treatment, leaching slag flotation treatment, iron slag pyrometallurgy treatment and the like, converts all metals of ore seeds into corresponding products, realizes comprehensive utilization of high-magnesium nickel sulfide ore, has low investment cost, and realizes low-cost and high-benefit treatment of high-magnesium nickel sulfide ore concentrate.
The technical scheme in the application is further described below with reference to specific embodiments:
the raw materials used in examples 1 to 10 were nickel sulfide ores whose main element components are shown in Table 1.
TABLE 1 principal elemental composition of Nickel sulfide mineral raw Material
| Nickel sulphide ore | Ni | Co | Cu | Fe | S | Mg |
| ％ | 8.5 | 0.4 | 1.9 | 40.1 | 35.7 | 5.2 |
Example 1
1000g of the nickel sulfide ore in the table 1 is leached for 2 hours under normal temperature by adopting a stirring tank, controlling the liquid-solid ratio to be 3:1 and the sulfuric acid concentration to be 60g/L, and the leaching result is shown in the table 2.
Example 2
1000g of the nickel sulfide ore in the table 1 is leached for 2 hours under normal temperature by adopting a stirring tank, controlling the liquid-solid ratio to be 3:1 and the sulfuric acid concentration to be 80g/L, and the leaching result is shown in the table 2.
Example 3
1000g of the nickel sulfide ore in the table 1 is leached for 2 hours under normal temperature by adopting a stirring tank, controlling the liquid-solid ratio to be 3:1 and the sulfuric acid concentration to be 100g/L, and the leaching result is shown in the table 2.
Table 2 results of pre-soaking magnesium removal
It can be seen from examples 1-3 that: when the concentration of sulfuric acid reaches 80g/L, about 90% of magnesium in the nickel sulfide is leached, and meanwhile, the leaching rate of nickel, cobalt, copper and iron is lower; when the sulfuric acid concentration is increased to 100g/L, the leaching rate of each metal is basically unchanged. Therefore, the nickel sulfide ore pre-impregnated with the sulfuric acid has good magnesium removal effect.
Example 4
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 5:1 and a ball milling strength of 15G; then, a vertical autoclave was used to carry out oxygen-enriched leaching for 3 hours under the conditions of a liquid-solid ratio of 4:1, a temperature of 120℃and an oxygen partial pressure of 0.5MPa, and the results are shown in Table 3.
Example 5
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 15G; then, a vertical autoclave was used to carry out oxygen-enriched leaching for 3 hours under the conditions of a liquid-solid ratio of 4:1, a temperature of 120℃and an oxygen partial pressure of 0.5MPa, and the results are shown in Table 3.
Example 6
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 35:1 and a ball milling strength of 15G; then, a vertical autoclave was used to carry out oxygen-enriched leaching for 3 hours under the conditions of a liquid-solid ratio of 4:1, a temperature of 120℃and an oxygen partial pressure of 0.5MPa, and the results are shown in Table 3.
TABLE 3 results of mechanical activation-oxygen-enriched leaching
| Leaching yield (%) | Ni | Co | Cu | Fe |
| Ball to material ratio 5:1 | 64.4 | 57.3 | 63.8 | 50.1 |
| Ball to material ratio 20:1 | 97.1 | 95.5 | 92.4 | 36.7 |
| Ball to material ratio of 35:1 | 96.7 | 95.8 | 91.6 | 44.1 |
It can be seen from examples 4-6 that: when the wet ball milling activation treatment is adopted, when the ball-material ratio reaches 20:1, the leaching rate of valuable metals such as nickel, cobalt, copper and the like is high, and the leaching rate of iron is lower; when the ball-to-charge ratio is increased to 35:1, the leaching rate of valuable metals is basically unchanged, and the leaching rate of impurity iron is greatly increased. Therefore, the leaching rate of valuable metals can be effectively improved by properly improving the ball-to-material ratio, and the leaching rate of impurity iron is controlled at a lower level.
Example 7
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 5G; then adopting a vertical autoclave, and carrying out oxygen-enriched leaching for 3 hours under the conditions of 4:1 liquid-solid ratio, 120 ℃ temperature and 0.5Mpa oxygen partial pressure. The results are shown in Table 4.
Example 8
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 15G; then adopting a vertical autoclave, and carrying out oxygen-enriched leaching for 3 hours under the conditions of 4:1 liquid-solid ratio, 120 ℃ temperature and 0.5Mpa oxygen partial pressure. The results are shown in Table 4.
Example 9
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 25G; then adopting a vertical autoclave, and carrying out oxygen-enriched leaching for 3 hours under the conditions of 4:1 liquid-solid ratio, 120 ℃ temperature and 0.5Mpa oxygen partial pressure. The results are shown in Table 4.
TABLE 4 results of mechanical activation-oxygen-enriched leaching
| Leaching yield (%) | Ni | Co | Cu | Fe |
| Ball milling intensity 5G | 72.4 | 45.2 | 76.6 | 51.3 |
| Ball milling intensity 15G | 97.1 | 95.5 | 92.4 | 36.7 |
| Ball milling intensity 25G | 96.6 | 94.4 | 92.2 | 37.1 |
It can be seen from examples 7 to 9 that: when wet ball milling activation treatment is adopted, when the ball milling strength is 15G, the leaching rate of valuable metals such as nickel, cobalt, copper and the like is high, and the leaching rate of iron is lower; when the ball milling strength is 25G, the leaching rate of each metal is basically unchanged. Therefore, the ball milling strength is properly improved, the leaching rate of valuable metals can be greatly improved, and most of impurity iron is remained in slag.
Example 10
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 15G; then adopting a vertical autoclave, and carrying out oxygen-enriched leaching for 3 hours under the conditions of a liquid-solid ratio of 4:1, a temperature of 100 ℃ and an oxygen partial pressure of 0.5 Mpa. The results are shown in Table 5.
Example 11
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 15G; then adopting a vertical autoclave, and carrying out oxygen-enriched leaching for 3 hours under the conditions of 4:1 liquid-solid ratio, 120 ℃ temperature and 0.5Mpa oxygen partial pressure. The results are shown in Table 5.
Example 12
1000G of leaching slag obtained after the pre-soaking magnesium removal in the embodiment 2 is subjected to wet grinding by adopting a ball mill, and ball milling is carried out for 2h under the conditions of a ball-to-material ratio of 20:1 and a ball milling strength of 15G; then adopting a vertical autoclave, and carrying out oxygen-enriched leaching for 3 hours under the conditions of a liquid-solid ratio of 4:1, a temperature of 140 ℃ and an oxygen partial pressure of 0.5 Mpa. The results are shown in Table 5.
TABLE 5 results of mechanical activation-oxygen-enriched leaching
| Leaching yield (%) | Ni | Co | Cu | Fe |
| Leaching at 100 DEG C | 88.9 | 86.7 | 89.2 | 30.2 |
| Leaching at 120 DEG C | 97.1 | 95.5 | 92.4 | 36.7 |
| Leaching at 140 DEG C | 97.3 | 95.8 | 92.7 | 63.2 |
It can be seen from examples 10 to 12 that: mechanical activation is carried out on the pre-soaked ore pulp after magnesium removal through wet ball milling, and the obtained ore pulp can be subjected to oxygen-enriched leaching at a lower temperature and has a beneficial leaching rate, wherein when the leaching rate is higher than 140 ℃, the leaching rate lifting amplitude is reduced, but the iron content is increased; thus, the oxygen-enriched leaching temperature is selected to be 100 ℃ to 140 ℃, more preferably 110 ℃ to 130 ℃.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (13)
1. A method for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen enrichment method is characterized by comprising the following steps:
taking high-magnesium nickel sulfide ore as a raw material, pre-soaking for removing magnesium to obtain magnesium-containing pre-soaking liquid and pre-soaking slag;
mechanically activating the presoaked slag by adopting a ball milling method to obtain activated ore pulp;
leaching the activated ore pulp by adopting a low-temperature oxygen-enriched method to obtain a leaching solution containing nickel and leaching residues;
and (3) carrying out post-treatment by adopting the nickel-containing leaching solution, and converting metals in the nickel-containing leaching solution into corresponding products.
2. The method for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method according to claim 1, wherein sulfuric acid is used as a leaching reagent when the magnesium is pre-soaked and removed, and liquid-solid separation is carried out after leaching for 0.5-3 h at normal temperature; wherein the concentration of sulfuric acid is 80 g/L-100 g/L; the addition amount of sulfuric acid is determined according to the magnesium oxide content of the high-magnesium nickel sulfide ore, and the liquid-solid ratio is controlled to be 2:1-5:1;
and/or after pre-soaking and magnesium removal, the leaching rate of magnesium oxide is more than or equal to 90%, the leaching rates of nickel, cobalt and copper in magnesium-containing pre-leaching liquid are all less than 5%, and the leaching rate of iron is less than 7%.
3. The method for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method according to claim 1, wherein the mechanical activation is performed by adopting a wet ball milling mode, wherein the ball-material ratio is 5:1-35:1, the ball milling strength is 5G-25G, and the ball milling time is 0.5 h-5 h.
4. The method for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen-enriched method according to claim 1, which is characterized in that when leaching is carried out by the low-temperature oxygen-enriched method, oxygen or oxygen enriched is introduced as a leaching oxidant, the reaction temperature is controlled to be 100-130 ℃, the reaction pressure is controlled to be 0.3-1.0 MPa, the liquid-solid ratio is 3:1-6:1, and liquid-solid separation is carried out after stirring and oxygen enriched leaching for 0.5-5 hours;
and/or leaching by a low-temperature oxygen-enriched method to obtain a nickel-containing leaching solution, wherein the leaching rate of nickel is more than or equal to 95%, the leaching rate of cobalt is more than or equal to 95%, the leaching rate of copper is more than or equal to 90%, and the leaching rate of iron is less than 40%.
5. The method for comprehensively utilizing high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method according to claim 1, wherein the nickel content in the high-magnesium nickel sulfide ore is 5% -15% and the magnesium oxide content is 6% -20%.
6. The method for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen enrichment method according to claim 1, wherein the post-treatment of the nickel-containing leaching solution comprises the following steps: sequentially removing copper, iron and nickel cobalt;
when copper is removed, an iron powder replacement method is adopted to remove copper from the nickel-containing leaching solution, so that sponge copper and copper-removed liquid are obtained; the addition amount of the iron powder is 1-3 times of the theoretical amount of copper, and the reaction time is 0.5-2 h after stirring at normal temperature.
7. The method for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method according to claim 6, wherein the method is characterized in that when iron is removed, a goethite method is adopted to remove iron from the copper-removed liquid to obtain an iron-removed liquid and iron slag; wherein, adopt goethite method to remove copper back liquid deironing, include: regulating the pH value of the solution after copper removal to 3-4, wherein nickel carbonate is adopted as a pH regulator; introducing oxygen or oxygen-enriched air as iron-removing oxidant, controlling reaction temperature at 70-90 deg.C, stirring, reacting for 2-10 hr, and then liquid-solid separation.
8. The method for comprehensively utilizing the high-magnesium nickel sulfide ore by the low-temperature oxygen enrichment method according to claim 7, which is characterized in that,
extracting the deironing liquid to obtain magnesium sulfate, cobalt sulfate products and nickel sulfate products, and sending the magnesium sulfate into evaporation crystallization; wherein, during extraction, P204 is adopted to extract nickel, and P507 is adopted to extract cobalt;
and/or, the method further comprises: and (3) carrying out nickel precipitation on the deironing solution by adopting sodium carbonate to generate nickel carbonate and sodium sulfate, and sending the nickel carbonate serving as a pH regulator of the goethite method into the deironing step.
9. The method for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen enrichment method according to claim 6, wherein the method further comprises the following steps:
neutralizing the magnesium-containing pre-leaching solution by using a neutralizing agent, carrying out solid-liquid separation, evaporating and crystallizing to obtain a magnesium sulfate product, and sending the neutralized slag obtained by neutralization into a leaching step by a low-temperature oxygen-enriched method; wherein the neutralizer is one or two of magnesium oxide and magnesium carbonate;
floating the leached slag to obtain sulfur concentrate and tailings;
and treating tailings and iron slag after iron removal by a pyrogenic process to obtain an iron ore product, and sending the generated sulfur dioxide flue gas to be used as a leaching reagent for pre-soaking and removing magnesium after acid production.
10. A system for a method for comprehensively utilizing high-magnesium nickel sulfide ore by a low-temperature oxygen enrichment method according to any one of claims 1-9, comprising:
the pre-soaking magnesium removing device is used for pre-soaking magnesium removing by taking high-magnesium nickel sulfide ore as a raw material to obtain magnesium-containing pre-soaking liquid and pre-soaking slag;
the mechanical activation device comprises a ball mill and is used for mechanically activating the presoaked slag obtained by the presoaking and demagging device to obtain activated ore pulp;
the low-temperature oxygen-enriched leaching device is used for leaching the activated ore pulp by adopting a low-temperature oxygen-enriched method to obtain a nickel-containing leaching solution and leaching slag;
the post-treatment device is used for carrying out post-treatment on the nickel-containing leaching solution and converting each metal into a corresponding product.
11. A system according to claim 10, wherein,
the pre-soaking magnesium removing device comprises a tank body, a stirrer and a first filtering device, wherein sulfuric acid is added into the tank body as a leaching reagent, the concentration of the sulfuric acid is 60 g/L-100 g/L, and when the pre-soaking magnesium removing device is used for pre-soaking, the liquid-solid ratio is 2:1-5:1, and the leaching is carried out for 0.5 h-3 h under normal temperature;
the ball mill of the mechanical activation device adopts a wet milling mode, the ball-material ratio is 5:1-35:1, the ball milling strength is 5G-25G, and the ball milling time is 0.5 h-5 h;
the low-temperature oxygen-enriched leaching device comprises a vertical autoclave and a second filtering device, wherein the vertical autoclave is provided with a leaching oxidant inlet, the temperature in the autoclave is 100-130 ℃, the pressure is 0.3-1.0 MPa, the liquid-solid ratio is 3:1-6:1 during leaching, and the stirring oxygen-enriched leaching is carried out for 0.5-5 h.
12. A system according to claim 10, wherein,
the post-treatment device for the leaching liquid containing nickel comprises: the copper removal unit, the goethite iron removal unit, the third filtering device and the extraction unit are sequentially arranged; the decoppering unit is used for decoppering the nickel-containing leaching solution by adopting an iron powder replacement method to obtain sponge copper and decoppered liquid; the goethite iron removal unit is used for removing iron from the copper-removed liquid by adopting a goethite method, and filtering the copper-removed liquid by the filtering unit to obtain iron-removed liquid and iron slag; the extraction unit adopts P204 to extract nickel and P507 to extract cobalt, so as to obtain a nickel cobalt product;
and/or, further comprising: and the nickel depositing device is respectively connected with the filtering unit and the goethite iron removing unit and is used for depositing nickel to the iron-removed liquid by adopting sodium carbonate to generate nickel carbonate and sodium sulfate, and sending the nickel carbonate into the goethite iron removing unit to be used as a goethite method pH regulator.
13. The system of claim 12, wherein the system further comprises:
the magnesium-containing pre-immersion liquid treatment device is connected with the first filtering device and comprises a neutralization unit, a fourth filtering device and an evaporative crystallization unit which are sequentially arranged, wherein the fourth filtering device is also connected with the low-temperature oxygen-enriched leaching device and is used for conveying the neutralization slag obtained by the neutralization unit into the low-temperature oxygen-enriched leaching device for treatment;
the flotation unit is connected with the second filtering device and is used for carrying out flotation on the leached slag after separation to obtain sulfur concentrate and tailings;
the pyrogenic process treatment unit is respectively connected with the flotation unit and the third filtering device and is used for carrying out pyrogenic process treatment on tailings and iron-removed iron slag to obtain iron ore products; the pyrogenic process unit is also connected with an acid making device which is connected with a pre-soaking magnesium removing device and is used for sending sulfur dioxide flue gas generated in the pyrogenic process to the pre-soaking magnesium removing device for use as a leaching reagent after making acid.
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