CN116240381A - Method for comprehensively utilizing laterite nickel ore leaching slag - Google Patents
Method for comprehensively utilizing laterite nickel ore leaching slag Download PDFInfo
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- CN116240381A CN116240381A CN202310094970.1A CN202310094970A CN116240381A CN 116240381 A CN116240381 A CN 116240381A CN 202310094970 A CN202310094970 A CN 202310094970A CN 116240381 A CN116240381 A CN 116240381A
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- acid
- leaching
- iron
- laterite
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000002386 leaching Methods 0.000 title claims abstract description 112
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 91
- 239000002893 slag Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910001710 laterite Inorganic materials 0.000 title claims abstract description 18
- 239000011504 laterite Substances 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 39
- 230000000996 additive effect Effects 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 30
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000007885 magnetic separation Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000002525 ultrasonication Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 154
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 18
- 150000004698 iron complex Chemical class 0.000 claims description 17
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910000863 Ferronickel Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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
-
- 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
- C22B23/0423—Halogenated 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
- C22B23/0407—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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric 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
- 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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Abstract
The invention provides a method for comprehensively utilizing leaching slag of laterite nickel ore, and belongs to the technical field of comprehensive utilization of industrial solid wastes. The method comprises the following steps: s1: acid leaching is carried out on the laterite nickel ore leaching residues to be treated by using acid 1, and leaching residues and leaching liquid are obtained after solid-liquid separation; s2: adding nano Fe into the leaching solution obtained in the step S1 3 O 4 Adding acid 2 into the seed crystal and the additive 1 to adjust the pH value of the mixed solution to 0-2, carrying out hydrothermal reaction, carrying out ultrasonic and magnetic separation on the obtained product after the reaction is finished, and carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1; s3: filtering the solution obtained in the step S2Concentrating the solution 1, adding alkali to adjust the pH of the concentrated solution to 7-12, and separating to obtain nickel salt. By using nano Fe 3 O 4 The crystal seeds are crystallized, so that Fe and Ni in the laterite-nickel ore leaching slag can be selectively separated, and the utilization value of the laterite-nickel ore can be fully exerted.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of industrial solid wastes, in particular to a method for comprehensively utilizing leaching residues of laterite nickel ores.
Background
The laterite-nickel ore contains a large amount of valuable metal elements such as nickel, iron and the like, and in order to improve the resource utilization rate, the elements must be maximally extracted from the laterite-nickel ore and the corresponding high added value products must be obtained. The main current method for extracting elements from laterite nickel ores at home and abroad is an acid leaching method, namely leaching nickel elements from the laterite nickel ores by sulfuric acid and the like. However, the main treatment of laterite nickel ore leaching residues is landfill, which wastes these valuable resources considerably. Under the background that resources such as Ni/Co/Fe and the like are still greatly required in the current lithium ion battery field, the maximum efficiency of utilizing the valuable elements from laterite-nickel ore leaching slag is very necessary.
Products such as ferric phosphate and nickel hydroxide are usually used as precursors of the positive electrode of the lithium ion battery, and the obtaining of products such as qualified ferric phosphate from laterite-nickel ore leaching residues greatly relieves the resource pressure in the field of the lithium ion battery. For laterite-nickel ore acid leaching residues, where the iron and nickel chemistry is similar, the difficulty is in the selective separation of iron and nickel. However, there is currently no systematic method for obtaining valuable elements from laterite-nickel ore leaching residues, and the problems of low product purity and low element recovery are generally faced. If the elements such as Fe and Ni in the laterite-nickel ore leaching slag can be separated in a high selectivity way, the utilization value of the laterite-nickel ore can be fully exerted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for comprehensively utilizing laterite-nickel ore leaching slag.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the method for comprehensively utilizing the laterite-nickel ore leaching slag comprises the following steps:
s1: acid leaching is carried out on the laterite nickel ore leaching residues to be treated by using acid 1, and leaching residues and leaching liquid are obtained after solid-liquid separation;
s2: adding nano Fe into the leaching solution obtained in the step S1 3 O 4 Adding acid 2 into the seed crystal and the additive 1 to adjust the pH value of the mixed solution to 0-2, carrying out hydrothermal reaction, carrying out ultrasonic and magnetic separation on the obtained product after the reaction is finished, and carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1;
s3: concentrating the filtrate 1 obtained in the step S2, adding alkali to adjust the pH of the concentrated solution to 8-12, and separating to obtain nickel salt.
The invention obtains the ferronickel leaching solution by acid leaching, and then nano Fe is added into the ferronickel leaching solution 3 O 4 Seed crystal and additive 1, nano Fe 3 O 4 The seed crystal can selectively induce iron ions in the nickel-iron leaching solution, and the iron ions are formed by Fe on the surface of the seed crystal 3 O 4 And by adjusting the pH value of the mixed solution, the hydrolysis of nickel is inhibited, thereby realizing the separation of nickel and iron; in the hydrothermal reaction, the additive 1 can activate the seed crystal surface to promote seed crystal growth. Fe obtained by hydrothermal reaction 3 O 4 The particle surface is adsorbed with non-magnetic component, and Fe can be treated by ultrasonic and magnetic separation simultaneously 3 O 4 Stripping nonmagnetic component on particle surface to improve Fe 3 O 4 Purity of the particles, fe 3 O 4 The purity of the particles is more than 99.5 percent, and the particles can be directly utilized without subsequent treatment; the obtained filtrate does not need to additionally carry out impurity removal procedure of iron ions in the subsequent treatment process, thereby reducing the recovery cost of nickelThe recycling process of the laterite-nickel ore leaching slag is shortened, and the utilization rate of the laterite-nickel ore leaching slag is greatly improved.
Preferably, in step S2, the pH is 1-2.
Preferably, in step S3, the pH is 8.5-10.5.
The purpose of the pH adjustment in step S3 is to precipitate nickel ions in the filtrate as Ni (OH) 2 When the pH is less than 8, nickel ions cannot be precipitated, and when the pH is more than 12, the method does not accord with the principle of economy and environmental protection; therefore, the inventor prefers pH to be 8.5-10.5, which is more beneficial to nickel ion precipitation and further improves nickel recovery rate.
Preferably, the nano Fe 3 O 4 The preparation method of the seed crystal comprises the following steps: adding the iron complex and the additive 2 into an organic solvent for hydrothermal reaction, performing solid-liquid separation after the reaction is finished, and performing annealing treatment on the obtained filter residues 2 to obtain nano Fe 3 O 4 Seed crystals, wherein the molar ratio of additive 2 to iron complex is 0.1-2:1.
The iron complex generates Fe under the strong reduction of the additive 2 3 O 4 The molar ratio of additive 2 to iron complex affects Fe 3 O 4 Size and dispersibility of seed crystal, when the molar ratio of additive 2 to iron complex is 0.1-2:1, in this range, fe as the molar ratio of additive 2 to iron complex increases 3 O 4 The smaller the size of the seed crystal, the better the dispersibility; further increasing the molar ratio of additive 2 to iron complex, fe 3 O 4 The seed crystal did not change significantly in size, but its dispersibility was deteriorated.
Preferably, at least one of the following (a) - (h):
(a) The iron complex is at least one of iron oleate, iron acetylacetonate and ferrocene; more preferably, the iron complex is at least one of iron oleate and iron acetylacetonate;
(b) The additive 2 is at least one of oleylamine, hydrazine and vinyl pyrrolidone; more preferably, the additive 2 is oleylamine;
(c) The organic solvent is at least one of ethanol, glycol, polyethylene glycol, oleic acid, anisole and benzyl ether; more preferably, the organic solvent is at least one of anisole and benzyl ether.
In the invention, the iron complex firstly generates FeO (OH) under the action of the additive to regenerate Fe 3 O 4 The nano particles are cured to obtain nano Fe 3 O 4 Seed crystal, because of the polarity difference of the organic solvent and the additive, the additive can act as a surfactant to be attached to Fe during the hydrothermal reaction 3 O 4 Nanoparticle surface, induction of Fe 3 O 4 Self-assembling the nano particles to obtain the monodisperse nano Fe 3 O 4 And (5) seed crystal.
Nano Fe 3 O 4 Raw material of seed crystal for nano Fe 3 O 4 The performance of the seed crystal has a certain influence, when the iron complex is at least one of iron oleate and iron acetylacetonate, the additive 2 is oleylamine, and the organic solvent is at least one of anisole and benzyl ether, nano Fe is obtained 3 O 4 The seed crystal has better dispersibility.
(d) The ratio of the total volume of the additive 2 and the organic solvent to the mass of the iron complex is 1-100mL/g;
(e) The hydrothermal reaction time is 3-24 hours; more preferably, the hydrothermal reaction time is 6 to 18 hours;
(f) The temperature of the hydrothermal reaction is 120-280 ℃; more preferably, the temperature of the hydrothermal reaction is 150-230 ℃;
the liquid-solid ratio (i.e. the ratio of the total volume of additive 2 and organic solvent to the mass of the iron complex), time and temperature of the hydrothermal reaction all affect the nano Fe 3 O 4 Seed crystal performance; when the liquid-solid ratio of the hydrothermal reaction is lower than 1mL/g, the time is lower than 3h or the temperature is lower than 120 ℃, the solid-liquid two phases cannot fully react, and the obtained nano Fe3O4 seed crystal has large size and low dispersibility and is not beneficial to subsequent use; when the liquid-solid ratio of the hydrothermal reaction is higher than 100mL/g, the time is longer than 24h or the temperature is higher than 280 ℃, the performance of the nano Fe3O4 seed crystal cannot be further improved, meanwhile, the energy consumption is increased, and the production cost is increased.
(g) The annealing temperature is 300-700 ℃; more preferably, the annealing temperature is 400-600 ℃;
(h) The annealing time is 1-24h; more preferably, the annealing time is 6-18 hours.
The invention further improves the nano Fe through annealing treatment 3 O 4 Crystallinity of the seed crystal; when the annealing temperature is less than 300 ℃, nanometer Fe 3 O 4 The seed crystal is not sufficiently aged, and the obtained crystallinity is poor; when the annealing temperature is higher than 700 ℃, fe is caused 3 O 4 The phase of (a) is converted into other phases. When the annealing temperature is 400-600 ℃, the annealing time is 6-18h, and nanometer Fe 3 O 4 The crystallinity of the seed crystal is better.
Preferably, in step S1, at least one of the following (a) - (e):
(a) The concentration of the acid 1 is 0.1-6M; more preferably, the concentration of the acid 1 is 1-3M;
(b) The acid 1 is at least one of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid; more preferably, the acid 1 is at least one of sulfuric acid and phosphoric acid;
(c) The molar ratio of the acid 1 to the iron in the laterite-nickel ore leaching slag is 0.1-3:1, a step of; more preferably, the molar ratio of the acid 1 to the iron in the laterite-nickel ore leaching slag is 0.5-1:1;
(d) The liquid-solid ratio of the acid 1 to the laterite-nickel ore leaching slag is 1-30mL/g; more preferably, the liquid-solid ratio of the acid 1 to the laterite-nickel ore leaching slag is 3-10mL/g;
(e) The acid leaching time is 1-12h; more preferably, the acid leaching time is 3-9 hours.
The invention selectively leaches the ferro-nickel element in the laterite-nickel ore leaching slag by controlling the acid leaching conditions. When the concentration of the acid 1 is less than 0.1M, the molar ratio of the iron in the acid 1 and the laterite-nickel ore leaching slag is less than 0.1, the liquid-solid ratio of the acid 1 and the laterite-nickel ore leaching slag is less than 1mL/g or the acid leaching time is less than 1h, the laterite-nickel slag cannot be fully dissolved, resulting in reduced recovery of iron and nickel; when the concentration of the acid 1 is more than 6M, the mole ratio of the iron in the acid 1 and the laterite-nickel ore leaching slag is more than 0.13 or the liquid-solid ratio of the acid 1 and the laterite-nickel ore leaching slag is more than 30mL/g, the consumption of the acid 1 is high, resulting in increased cost and reduced treatment efficiency; further increasing the acid leaching time does not increase the leaching rate of iron and nickel.
Preferably, in step S2, the nano Fe 3 O 4 The molar ratio of the seed crystal to the iron in the leaching solution is 0.1-1:1; the molar ratio of the additive 1 to the iron in the leaching solution is 0.01-1:1. More preferably, the nano Fe 3 O 4 The molar ratio of the seed crystal to the iron in the leaching solution is 0.2-0.5:1; the molar ratio of the additive 1 to the iron in the leaching solution is 0.1-0.3:1.
The mole ratio of the nano iron oxide seed crystal to the iron in the leaching solution, the mole ratio of the additive 1 to the iron in the leaching solution affect the recovery rate of the iron in the leaching solution, and within the range, the recovery rate of the iron is high, the mole ratio of the nano iron oxide seed crystal to the iron in the leaching solution is less than 0.1 or the mole ratio of the additive 1 to the iron in the leaching solution is less than 0.01, and the iron in the leaching solution cannot be converted into Fe 3 O 4 Cannot be separated from nickel; nano Fe 3 O 4 The mole ratio of the seed crystal to the iron in the leaching solution is more than 1 or the mole ratio of the additive 1 to the iron in the leaching solution is more than 1, so that the treatment efficiency is reduced.
Preferably, in step S2, the additive 1 is at least one of oleylamine, hydrazine, and vinylpyrrolidone; the acid 2 is at least one of formic acid, phosphoric acid, boric acid, sulfurous acid, oxalic acid, acetic acid, citric acid and ascorbic acid. More preferably, the additive 1 is oleylamine.
Preferably, in step S2, the temperature of the hydrothermal reaction is 120-280 ℃, and the time of the hydrothermal reaction is 1-24 hours. More preferably, the temperature of the hydrothermal reaction is 150-230 ℃, and the time of the hydrothermal reaction is 3-9h.
Preferably, in step S2, the time of the ultrasound is 0.1-6h; the magnetic field intensity of the magnetic separation is 10-1200G. More preferably, the time of the ultrasound is 0.5-3 hours; the magnetic field intensity of the magnetic separation is 10-600G.
Within the above magnetic field intensity range, fe can be contained 3 O 4 Selectively separating, the magnetic field intensity is lower than 10G, fe 3 O 4 Cannot be separated; the magnetic field strength is higher than 1200G, and can notIncrease Fe 3 O 4 And increases the processing cost.
Preferably, in step S3, the alkali is at least one of ammonia water, sodium hydroxide, potassium hydroxide, and calcium hydroxide. More preferably, the base is sodium hydroxide.
Preferably, in step S3, the mass concentration of nickel in the concentrated solution is more than 30g/L.
Compared with the prior art, the invention has the beneficial effects that:
(1) By the method, the ferroferric oxide and nickel compounds with high purity can be obtained, the recovery rate of iron is more than 98.5%, the recovery rate of nickel is more than 98%, the purity of ferroferric oxide is more than 99.5%, the ferroferric oxide can be directly utilized without post-treatment, and the utilization rate of laterite-nickel ore leaching residues is remarkably improved.
(2) According to the invention, iron and nickel in the laterite-nickel ore leaching slag are separated through crystallization, the obtained nickel-containing filtrate almost contains no iron ions, the step of further removing iron is avoided, and the treatment flow of the laterite-nickel ore leaching slag is greatly reduced.
Drawings
FIG. 1 shows nano Fe obtained in example 1 3 O 4 Scanning electron microscope images of seed crystals;
fig. 2 is a scanning electron microscope image of the residue 1 obtained in example 1.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples and the accompanying drawings.
The main element contents in the laterite-nickel ore leaching slag used in the invention are shown in table 1.
TABLE 1 content of main elements in laterite Nickel ore leaching slag
| Main element | Fe | Ni | Ca | Mg | Si |
| Content (wt.) | 58.37 | 0.052 | 0.086 | 0.021 | 0.374 |
Example 1
The embodiment provides a method for comprehensively utilizing leaching slag of laterite nickel ore, which comprises the following steps:
s1: leaching 10g of laterite-nickel ore leaching slag with 100mL of sulfuric acid with the concentration of 1.5M for 6 hours, and carrying out solid-liquid separation to obtain leaching slag 1 and leaching liquid 1;
S2：
preparation of nano Fe 3 O 4 Seed crystal: 1M iron oleate is added into 100mL anisole, then 0.2M oleylamine is added, and the obtained mixture is subjected to hydrothermal reaction at 160 ℃ for 6 hours; after the reaction is finished, carrying out solid-liquid separation, and annealing the obtained filter residue 2 at 500 ℃ for 12 hours to obtain the monodisperse nano Fe 3 O 4 Seed crystal;
selective separation of iron: 7.3g of monodisperse nano Fe is added into the leaching solution 1 obtained in the step S1 3 O 4 Seed crystal and oleylamine with the amount of 0.011mol are added with formic acid to adjust the pH value of the mixed solution to 1.2, and then the mixture is subjected to hydrothermal reaction for 12 hours at 180 ℃; ultrasonic treatment is carried out on the product obtained after the reaction is finished for 1h, and a 180G magnetic field is applied simultaneously to obtain nano Fe 3 O 4 Particles and non-magnetic solutions; carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1; wherein, the filter residue 1 is an impurity, and the filtrate 1 is a nickel-containing solution;
s3: concentrating the filtrate 1 obtained in the step S2 until the nickel concentration in the concentrated solution is 35g/L, adding a sodium hydroxide aqueous solution to adjust the pH of the concentrated solution to 8.5, and obtaining a precipitate as nickel salt.
Example 2
The embodiment provides a method for comprehensively utilizing leaching slag of laterite nickel ore, which comprises the following steps:
s1: leaching 20g of laterite-nickel ore leaching slag with 160mL of hydrochloric acid with the concentration of 2M for 3 hours, and carrying out solid-liquid separation to obtain leaching slag 1 and leaching liquid 1;
S2：
preparation of nano Fe 3 O 4 Seed crystal: 1M ferric acetylacetonate is added into 50mL anisole, then 0.6M oleylamine is added, and the obtained mixture is subjected to hydrothermal reaction at 180 ℃ for 10 hours; after the reaction is finished, carrying out solid-liquid separation, and annealing the obtained filter residue 2 at 420 ℃ for 6 hours to obtain the monodisperse nano Fe 3 O 4 Seed crystal;
selective separation of iron: 24g of monodisperse nano Fe is added into the leaching solution 1 obtained in the step S1 3 O 4 Seed crystal and hydrazine with the amount of 0.04mol, adding phosphoric acid to adjust the pH value of the mixed solution to 1.5, and carrying out hydrothermal reaction for 18h at 200 ℃; ultrasonic treatment is carried out on the product obtained after the reaction is finished for 2 hours, and a 100G magnetic field is applied simultaneously to obtain nano Fe 3 O 4 Particles and non-magnetic solutions; carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1; wherein, the filter residue 1 is an impurity, and the filtrate 1 is a nickel-containing solution;
s3: concentrating the filtrate 1 obtained in the step S2 until the nickel concentration in the concentrated solution is 30g/L, adding a sodium hydroxide aqueous solution to adjust the pH of the concentrated solution to 10.5, and obtaining a precipitate as nickel salt.
Example 3
The embodiment provides a method for comprehensively utilizing leaching slag of laterite nickel ore, which comprises the following steps:
s1: leaching 5g of laterite-nickel ore leaching slag with 15mL of phosphoric acid with the concentration of 3M for 5h, and carrying out solid-liquid separation to obtain leaching slag 1 and leaching liquid 1;
S2：
preparation of nano Fe 3 O 4 Seed crystal: 1M ferrocene was added to 80mL ethanol, then 0.3M vinylpyrrolidone was added, and the resulting mixture was hydrothermally reacted at 200℃for 18 hours; after the reaction is finished, carrying out solid-liquid separation, and annealing the obtained filter residue 2 at 600 ℃ for 18 hours to obtain the monodisperse nano Fe 3 O 4 Seed crystal;
selective separation of iron: adding 2.4g of monodisperse nano Fe into the leaching solution 1 obtained in the step S1 3 O 4 Seed crystal and vinyl pyrrolidone with the amount of 0.01mol are added into the mixture, oxalic acid is added into the mixture to adjust the pH value of the mixture to be 1.8, and the mixture is subjected to hydrothermal reaction for 9 hours at 220 ℃; ultrasonic treatment is carried out on the product obtained after the reaction is finished for 3 hours, and a magnetic field of 300G is applied simultaneously to obtain nano Fe 3 O 4 Particles and non-magnetic solutions; carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1; wherein, the filter residue 1 is an impurity, and the filtrate 1 is a nickel-containing solution;
s3: concentrating the filtrate 1 obtained in the step S2 until the nickel concentration in the concentrated solution is 40g/L, adding a sodium hydroxide aqueous solution to adjust the pH of the concentrated solution to 9, and obtaining a precipitate as nickel salt.
Example 4
The embodiment provides a method for comprehensively utilizing leaching slag of laterite nickel ore, which comprises the following steps:
s1: leaching 10g of laterite-nickel ore leaching slag by using 50mL of nitric acid with the concentration of 1M for 8 hours, and carrying out solid-liquid separation to obtain leaching slag 1 and leaching liquid 1;
S2：
preparation of nano Fe 3 O 4 Seed crystal: 1M iron oleate was added to 30mL oleic acid, then 0.4M oleylamine was added, and the resulting mixture was hydrothermally reacted at 230℃for 12h; after the reaction is finished, carrying out solid-liquid separation, and annealing the obtained filter residue 2 at 560 ℃ for 9 hours to obtain the monodisperse nano Fe 3 O 4 Seed crystal;
selective separation of iron: adding 6.1g of monodisperse nano Fe into the leaching solution 1 obtained in the step S1 3 O 4 Seed crystal and oleylamine with the amount of 0.03mol, adding acetic acid to adjust the pH value of the mixed solution to 1, and carrying out hydrothermal reaction for 6h at 160 ℃; ultrasonic treatment is carried out on the product obtained after the reaction is finished for 0.5h, and a 450G magnetic field is applied simultaneously to obtain nano Fe 3 O 4 Particles and non-magnetic solutions; carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1; wherein, the filter residue 1 is an impurity, and the filtrate 1 is a nickel-containing solution;
s3: concentrating the filtrate 1 obtained in the step S2 until the nickel concentration in the concentrated solution is 36g/L, adding a sodium hydroxide aqueous solution to adjust the pH of the concentrated solution to 9.5, and obtaining a precipitate as nickel salt.
Example 5
The embodiment provides a method for comprehensively utilizing leaching slag of laterite nickel ore, which comprises the following steps:
s1: leaching 15g of laterite-nickel ore leaching slag with 90mL of hydrochloric acid with the concentration of 1.2M for 9h, and carrying out solid-liquid separation to obtain leaching slag 1 and leaching liquid 1;
S2：
preparation of nano Fe 3 O 4 Seed crystal: 1M ferric acetylacetonate was added to 40mL benzyl methyl ether, followed by 0.5M oleylamine, and the resulting mixture was hydrothermally reacted at 160℃for 6h; after the reaction is finished, carrying out solid-liquid separation, and annealing the obtained filter residue 2 at 500 ℃ for 12 hours to obtain the monodisperse nano Fe 3 O 4 Seed crystal;
selective separation of iron: adding 14.5g of monodisperse nano Fe into the leaching solution 1 obtained in the step S1 3 O 4 Seed crystal and oleylamine with the amount of 0.04mol, adding boric acid to adjust the pH value of the mixed solution to 2, and carrying out hydrothermal reaction for 15h at 230 ℃; ultrasonic treatment is carried out on the product obtained after the reaction is finished for 1.5 hours, and a 600G magnetic field is applied simultaneously to obtain nano Fe 3 O 4 Particles and non-magnetic solutions; carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1; wherein, the filter residue 1 is an impurity, and the filtrate 1 is a nickel-containing solution;
s3: concentrating the filtrate 1 obtained in the step S2 until the nickel concentration in the concentrated solution is 40g/L, adding a sodium hydroxide aqueous solution to adjust the pH of the concentrated solution to 10, and obtaining a precipitate as nickel salt.
Comparative example 1
The present comparative example provides a method for comprehensive utilization of laterite-nickel ore leaching slag, and the only difference between the present comparative example and example 1 is that: preparation of nano Fe 3 O 4 Additive 2 was not added during seeding.
Comparative example 2
The present comparative example provides a method for comprehensive utilization of laterite-nickel ore leaching slag, and the only difference between the present comparative example and example 1 is that: additive 1 was not added during the selective separation of iron.
Comparative example 3
The present comparative example provides a method for comprehensive utilization of laterite-nickel ore leaching slag, and the only difference between the present comparative example and example 1 is that: commercial magnet powder is used for replacing monodisperse nano Fe in the process of selectively separating iron 3 O 4 And (5) seed crystal.
Comparative example 4
The present comparative example provides a method for comprehensive utilization of laterite-nickel ore leaching slag, and the only difference between the present comparative example and example 1 is that: additive 2 in the process of selectively separating iron is sodium dodecyl benzene sulfonate.
Effect example
Calculating the recovery rate of nickel-iron element based on the content of nickel-iron element in the leaching residue of laterite nickel ore, and the obtained results are shown in Table 2; nanometer Fe is calculated based on ferronickel element content of laterite nickel ore leaching slag 3 O 4 The purity of the particles and nickel salt was as shown in Table 3.
Table 2 recovery of iron and nickel in each of the examples and comparative examples
TABLE 3 purity of recovered products obtained in examples and comparative examples
From tables 2 and 3, it can be seen thatThe method of the invention is used for recycling the laterite-nickel ore leaching slag, the recovery rate of iron can reach 99.5%, the recovery rate of nickel can reach 98.5%, and the obtained recovery product (ferroferric oxide and nickel salt) has high purity and can be directly utilized. Preparation of nano Fe 3 O 4 In the process of seed crystal or selective separation of iron, no additive is added, the recovery rate of iron and nickel is remarkably reduced, and the purity of the obtained recovered product is also reduced. Compared with commercial magnetic iron powder, the nano Fe prepared by the invention 3 O 4 The seed crystal can effectively and selectively separate iron from the leaching solution, thereby improving the recovery rate of the iron. Compared with other additives, in the process of selectively separating iron, at least one of oleylamine, hydrazine and vinyl pyrrolidone is selected as the additive, so that the recovery rate of iron and nickel can be remarkably improved, and the purity of the recovered product can be improved.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that the technical scheme of the invention may be modified or equally substituted without departing from the spirit and scope of the technical scheme of the invention.
Claims (10)
1. The method for comprehensively utilizing the laterite-nickel ore leaching slag is characterized by comprising the following steps of:
s1: acid leaching is carried out on the laterite nickel ore leaching residues to be treated by using acid 1, and leaching residues and leaching liquid are obtained after solid-liquid separation;
s2: adding nano Fe into the leaching solution obtained in the step S1 3 O 4 Adding acid 2 into the seed crystal and the additive 1 to adjust the pH value of the mixed solution to 0-2, carrying out hydrothermal reaction, carrying out ultrasonic and magnetic separation on the obtained product after the reaction is finished, and carrying out solid-liquid separation on the obtained nonmagnetic solution to obtain filter residue 1 and filtrate 1;
s3: concentrating the filtrate 1 obtained in the step S2, adding alkali to adjust the pH of the concentrated solution to 7-12, and separating to obtain nickel salt.
2. The method of claim 1, wherein the nano Fe 3 O 4 The preparation method of the seed crystal comprises the following steps: adding the iron complex and the additive 2 into an organic solvent for hydrothermal reaction, performing solid-liquid separation after the reaction is finished, and performing annealing treatment on the obtained filter residues 2 to obtain nano Fe 3 O 4 Seed crystals, wherein the molar ratio of additive 2 to iron complex is 0.1-2:1.
3. The method of claim 2, wherein at least one of the following (a) - (h):
(a) The iron complex is at least one of iron oleate, iron acetylacetonate and ferrocene;
(b) The additive 2 is at least one of oleylamine, hydrazine and vinyl pyrrolidone;
(c) The organic solvent is at least one of ethanol, glycol, polyethylene glycol, oleic acid, anisole and benzyl ether;
(d) The temperature of the hydrothermal reaction is 120-280 ℃;
(e) The hydrothermal reaction time is 3-24 hours;
(f) The ratio of the total volume of the additive 2 and the organic solvent to the mass of the iron complex is 1-100mL/g;
(g) The annealing temperature is 300-700 ℃;
(h) The annealing time is 1-24h.
4. The method of claim 1, wherein in step S1, at least one of the following (a) - (e):
(a) The concentration of the acid 1 is 0.1-6M;
(b) The acid 1 is at least one of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid;
(c) The molar ratio of the acid 1 to the iron in the laterite-nickel ore leaching slag is 0.1-3:1;
(d) The liquid-solid ratio of the acid 1 to the laterite-nickel ore leaching slag is 1-30mL/g;
(e) The acid leaching time is 1-12h.
5. The method of claim 1, wherein in step S2, the nano Fe 3 O 4 The mole ratio of the seed crystal to the iron in the leaching solution is 0.1-1:1, a step of; the molar ratio of the additive 1 to the iron in the leaching solution is 0.01-1:1.
6. The method of claim 1, wherein in step S2, the additive 1 is at least one of oleylamine, hydrazine, and vinylpyrrolidone; the acid 2 is at least one of formic acid, phosphoric acid, boric acid, sulfurous acid, oxalic acid, acetic acid, citric acid and ascorbic acid.
7. The method according to claim 1, wherein in step S2, the temperature of the hydrothermal reaction is 120 to 280 ℃, and the time of the hydrothermal reaction is 1 to 24 hours.
8. The method of claim 1, wherein in step S2, the time of the ultrasound is 0.5-3 hours; the magnetic field intensity of the magnetic separation is 10-1200G.
9. The method of claim 1, wherein in step S3, the base is at least one of ammonia, sodium hydroxide, potassium hydroxide, and calcium hydroxide.
10. The method of claim 1, wherein in step S3, the mass concentration of nickel in the concentrate is greater than 30g/L.
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| CN202310094970.1A CN116240381A (en) | 2023-02-07 | 2023-02-07 | Method for comprehensively utilizing laterite nickel ore leaching slag |
| PCT/CN2023/083925 WO2024164406A1 (en) | 2023-02-07 | 2023-03-26 | Method for comprehensive utilization of laterite nickel ore leaching residues |
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| CN108823430B (en) * | 2018-07-11 | 2020-04-28 | 山东大学 | Method for promoting laterite-nickel ore to leach nickel and cobalt by using surfactant |
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| CN113939478A (en) * | 2019-06-12 | 2022-01-14 | 川崎重工业株式会社 | Method and apparatus for producing vanadium compound, and method and apparatus for producing redox flow battery electrolyte |
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