CN117004816A - Method for separating ferronickel by chloridizing roasting of ferronickel alloy - Google Patents
Method for separating ferronickel by chloridizing roasting of ferronickel alloy Download PDFInfo
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- CN117004816A CN117004816A CN202310970699.3A CN202310970699A CN117004816A CN 117004816 A CN117004816 A CN 117004816A CN 202310970699 A CN202310970699 A CN 202310970699A CN 117004816 A CN117004816 A CN 117004816A
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- roasting
- ferronickel
- nickel
- iron
- alloy
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- 229910000863 Ferronickel Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 66
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 49
- 239000000956 alloy Substances 0.000 title claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 107
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- 239000000460 chlorine Substances 0.000 claims abstract description 41
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 36
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 35
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 28
- 238000009833 condensation Methods 0.000 claims abstract description 25
- 230000005494 condensation Effects 0.000 claims abstract description 25
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 238000002386 leaching Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000005955 Ferric phosphate Substances 0.000 description 10
- 229940032958 ferric phosphate Drugs 0.000 description 10
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 10
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- -1 preferably Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10715—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material
- C01B33/10721—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material with the preferential formation of tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- 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
- C22B23/02—Obtaining nickel or cobalt by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/001—Dry processes
- C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Abstract
The invention discloses a method for separating ferronickel by chloridizing roasting of ferronickel alloy, which comprises the following steps: (1) disposing a nickel-iron alloy in a roasting furnace; (2) Introducing a gaseous chlorinating agent into a roasting furnace for sectional roasting to obtain roasting slag and a roasting gas phase; wherein the gaseous chlorinating agent is a mixture of chlorine and gaseous ferric chloride; (3) And (3) carrying out sectional condensation on the roasting gas phase obtained in the step (2) to obtain solid ferric chloride and liquid silicon tetrachloride respectively. The invention realizes the selective directional volatilization of iron into gas phase by controlling the composition of chlorinating agent in the chloridizing roasting process, simultaneously ensures that nickel is not chloridized, can realize the separation of nickel and iron in the nickel-iron alloy by only one step, and has short process flow.
Description
Technical Field
The invention belongs to the field of resource utilization, and particularly relates to a method for separating ferronickel by chloridizing roasting of ferronickel alloy.
Background
Nickel is called "industrial vitamin" and is widely used in the sectors of industrial machinery manufacturing, aerospace, atomic energy reactors, etc.; nickel is also an important raw material for various batteries such as nickel-hydrogen batteries, nickel-cadmium batteries, ternary material lithium ion batteries and the like, and has wide application in the fields of portable equipment, electric automobiles, energy storage batteries and the like. At present, 70% of nickel is used in the stainless steel consumption field, 16% of nickel is used in other alloys except stainless steel, 8% of nickel is used for protecting decorative coating, and the nickel consumption ratio in the battery field is only 5%. However, with the rapid development of the global electric automobile industry, the consumption rate of nickel in the stainless steel field in 2030 is expected to be reduced from 70% to 52% at present, and the consumption rate of the battery department is expected to be increased from 5% to 31%. It can be seen that the supply of ferronickel raw materials obtained based on the mature laterite-nickel ore smelting process to industries other than stainless steel, such as the electric automobile industry, is a key to ensuring the balance of nickel supply and demand in each industry. However, the iron content in the ferronickel alloy is very high, and development of an efficient separation process of the iron in the ferronickel alloy is urgently needed to obtain nickel-rich powder.
The patent application No. CN202310067518.6 discloses a method for preparing battery-grade ferric phosphate by utilizing nickel-iron alloy, which comprises the steps of heating and acid-dissolving nickel-iron alloy, then reacting leaching liquid with complexing agent, ferric phosphate seed crystal, phosphoric acid and oxidant to obtain ferric phosphate dihydrate precipitate, washing with hot water, and finally mixing with reducing agent to perform solid-phase oxidation reaction to prepare battery-grade ferric phosphate; by adding complexing agent, ni (NH) 3 ) 4 ] 2+ The group is used for effectively removing nickel ions, so that the nickel ions are prevented from entering the ferric phosphate crystal lattice in the preparation process of the ferric phosphate, and the possibility that the nickel ions are adsorbed by the ferric phosphate is reduced. Patent application No. CN202211585186.2 discloses a method for jointly treating laterite-nickel ore and nickel-iron alloy and recovering nickel and iron, which utilizes normal pressure leaching solution of laterite-nickel ore to obtain high acid and Fe-enriched solution 3+ The characteristic of (2) is to treat the nickel-iron alloy, not only the residual acid in the leaching solution is neutralized by the nickel-iron, but also the residual acid and Fe in the leaching solution are utilized 3+ The strong oxidizing property of the nickel-iron alloy promotes the dissolution of nickel-iron, realizes the high-efficiency recovery of nickel and iron, and finally obtains the ferric phosphate and the battery-grade nickel sulfate.Patent application number CN202211380295.0 discloses a method for extracting iron from nickel-iron alloy and preparing hydrogen peroxide, which uses sulfuric acid to leach the nickel-iron alloy, collects tail gas generated by slurry heating reaction in the leaching process, carries out desulfurization and purification operation to recover hydrogen, purifies the hydrogen and then is used for preparing hydrogen peroxide. Patent application number CN202211252938.3 discloses a method for preparing nickel sulfate by using ferronickel alloy powder, which comprises the steps of mixing the ferronickel alloy powder with concentrated sulfuric acid, roasting twice, grinding the roasted material, adding water into the ground material for leaching, and carrying out liquid-solid separation to obtain nickel sulfate solution and iron slag. The method is characterized in that the nickel sulfate solution is obtained by water immersion after acid mixing and roasting. The patent application No. CN202211191569.1 discloses a preparation method for producing battery grade ferric phosphate by adopting an iron-based nickel-containing alloy, which mainly comprises the steps of acid leaching nickel-iron alloy powder to obtain a leaching solution, and removing impurities to obtain an iron-containing solution for preparing ferric phosphate. The patent application No. CN202211126429.6 discloses a method for preparing lithium iron phosphate by using nickel-iron alloy and application thereof, wherein the nickel-iron alloy is leached by adopting a mode of combining organic acid and oxidant, then ferric salt and nickel salt in the nickel-iron alloy are precipitated step by adopting an organic precipitator, ferric salt precipitation can be directly used for preparing lithium iron phosphate, and nickel salt precipitation can be used as a nickel source for preparing a subsequent ternary positive electrode material.
Therefore, the method for utilizing the nickel-iron alloy at high value mainly comprises the steps of firstly adopting a reagent to carry out wet leaching on the nickel-iron alloy so as to destroy the compact structure of the nickel-iron alloy, enabling nickel, iron and the like in the alloy to enter a solution, and then carrying out impurity removal and purification on the solution to partially extract valuable metals. When the nickel-iron alloy is leached by the method, both nickel and iron enter the leaching solution, and the leaching solution is not selective, so that the subsequent lengthy extraction procedures such as impurity removal, separation and the like are caused.
Disclosure of Invention
The invention aims to solve the technical problems of difficult nickel and iron separation, long process flow, complex process and the like in the existing nickel-iron alloy high-value utilization process.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the method for separating ferronickel by chloridizing roasting ferronickel alloy comprises the following steps:
(1) Disposing a nickel-iron alloy in a roasting furnace;
(2) Introducing a gaseous chlorinating agent into a roasting furnace for sectional roasting to obtain roasting slag and a roasting gas phase; wherein the gaseous chlorinating agent is a mixture of chlorine and gaseous ferric chloride;
(3) And (3) carrying out sectional condensation on the roasting gas phase obtained in the step (2) to obtain solid ferric chloride and liquid silicon tetrachloride respectively.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, in the step (2), the sectional roasting is divided into two sections of roasting, wherein the roasting temperature of one section of roasting is 550-690 ℃, and the roasting time is 5-15 min; the roasting temperature of the second-stage roasting is 550-750 ℃ and the roasting time is 30-180 min.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, in the step (2), the molar ratio of the chlorine in the gaseous chlorinating agent to the iron in the ferronickel alloy is 1:5-1:10 in the first-stage roasting process.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, in the step (2), the molar ratio of the chlorine in the gaseous chlorinating agent to the iron in the ferronickel alloy is 3:1-60:1 in the two-stage roasting process.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, in the step (2), the molar ratio of chlorine in the gaseous chlorinating agent to gaseous ferric chloride in the first-stage roasting process is not higher than 0.5.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, in the step (2), in the two-stage roasting process, the molar ratio of chlorine in the gaseous chlorinating agent to gaseous ferric chloride is 8-15.
In the above method for separating ferronickel by chloridizing roasting of ferronickel alloy, preferably, in the step (3), the sectional condensation means that the roasting gas phase is first subjected to first-stage condensation at 80-260 ℃ and then is subjected to second-stage condensation at 25-30 ℃.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, ball milling treatment is carried out on roasting slag obtained in the step (2) to obtain nickel-rich powder.
In the method for separating ferronickel by chloridizing roasting the ferronickel, preferably, in the step (1), the granularity of the ferronickel is 0.3-4 cm.
In the method for separating ferronickel by chloridizing roasting of the ferronickel alloy, preferably, argon is used for exhausting air in a roasting furnace before roasting in the step (2).
The invention realizes the selective directional volatilization of iron by controlling the composition of the chlorinating agent and the roasting temperature in the chloridizing roasting process, and simultaneously ensures that nickel is not chloridized. The main principle is that by regulating the composition of the chlorinating agent, a ferrous chloride solid film or ferrous chloride liquid film is formed on the surface of the nickel-iron alloy preferentially, the solid film or liquid film can effectively control the reaction rate and the course of the chlorination process, a reaction intermediate medium is provided, and further, the chlorination and volatilization loss of nickel in the nickel-iron alloy are avoided, and the main related principle is as follows:
construction of the membrane: in the stage, the mol ratio of chlorine in the gaseous chlorinating agent to gaseous ferric chloride is controlled to be not higher than 0.5, and the main reaction is realized by controlling the ratio of chlorine in the chlorinating agent to ferric chloride: feCl 3 (g)+Fe→FeCl 2 (l) Or FeCl 3 +Fe→FeCl 2 (s)，Cl 2 (g)+Fe→FeCl 2 (l) Or Cl 2 +Fe→FeCl 2 (s); with a small amount of Cl 2 (g)+Fe→FeCl 3 (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite As the reaction is mainly carried out on the surface of the ferronickel particles at the initial stage, the generated solid or liquid ferrous chloride film can be adhered to the surface of the ferronickel to form an intermediate transition layer, and meanwhile, a small amount of Cl is contained 2 (g)+Fe→FeCl 3 (g) The reaction, the generation of ferric chloride gas can make the transition layer have a certain gap.
Directional chlorination volatilization of iron: in this stage, the molar ratio of chlorine to gaseous ferric chloride in the gaseous chlorinating agent is 8-15. Chlorine gas contacts with the intermediate transition layer to make the mainThe reaction is as follows: feCl 2 (s/l)+Cl 2 (g)→FeCl 3 (g) The volatilization of ferrous chloride in the solid or liquid ferrous chloride film is initiated. But at the same time due to FeCl 3 (g)+Fe→FeCl 2 (l) Or FeCl 3 +Fe→FeCl 2 (s)，Cl 2 (g)+Fe→FeCl 2 (l) Or Cl 2 +Fe→FeCl 2 (s) is synchronously carried out, thereby ensuring that the surface of the nickel-iron alloy always has a transition layer, leading the volatilization of iron to mainly occur in the transition layer, further effectively inhibiting the reaction rate, reducing the local overheating, preventing the chlorination of nickel and the outward volatilization of nickel (NiCl) 2 The boiling point is 973 ℃ and the initial volatilization temperature is 671 ℃, so that the directional volatilization of iron in the ferronickel alloy is realized, and nickel still remains in the slag in the form of metallic nickel.
Compared with the prior art, the invention has the advantages that:
(1) The invention realizes the selective directional volatilization of iron into gas phase by controlling the composition of chlorinating agent in the chloridizing roasting process, simultaneously ensures that nickel is not chloridized, can realize the separation of nickel and iron in the nickel-iron alloy by only one step, and has short process flow.
(2) The method has high recycling utilization rate, the iron volatilization rate is up to more than 90 percent, the volatilized iron can obtain a high-quality ferric chloride product through condensation, nickel is not volatilized, the nickel is still remained in the slag in a particle form, the slag is easy to grind into powder, and the powder can be used as a nickel front end raw material required by the production of a power battery.
Drawings
FIG. 1 is a process flow diagram of separating ferronickel by chloridizing roasting of ferronickel alloy in the invention.
FIG. 2 is a phase analysis diagram of the nickel rich powder obtained in example 2 of the present invention.
FIG. 3 is a phase analysis diagram of the nickel rich powder obtained in example 3 of the present invention.
FIG. 4 is a graph showing phase analysis of the calcined product obtained by the condition test of group a in comparative example 1 of the present invention.
FIG. 5 is a graph showing phase analysis of the calcined product obtained by the condition test of group b in comparative example 1 of the present invention.
FIG. 6 is a graph showing phase analysis of the calcined product obtained by the c-group condition experiment in comparative example 1 of the present invention.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
The various reagents and materials used in the present invention are commercially available or may be prepared by known methods unless otherwise specified.
The composition and particle size of the nickel-iron alloys treated in the following examples and comparative examples are shown in table 1.
Table 1: chemical composition (wt%) of nickel-iron alloy
The gaseous ferric trichloride in the examples below was formed by heating ferric trichloride in a furnace.
Example 1:
the invention relates to a method for separating ferronickel by chloridizing roasting of ferronickel alloy, which has the process flow shown in figure 1 and comprises the following steps:
(1) The ferronickel alloy iron particles with the granularity of 1-2 cm are naturally piled up and arranged in a roasting furnace, and then argon is introduced to exhaust the air in the furnace.
(2) Introducing a chlorinating agent into the roasting furnace for one-stage roasting, wherein the chlorinating agent is chlorine and gaseous ferric trichloride, the molar ratio of the chlorine to the gaseous ferric trichloride is 0.1, the molar ratio of the chlorine in the chlorinating agent to the iron in the ferronickel alloy is 1:5, and the one-stage roasting temperature is controlled to be 600 ℃ and the roasting is carried out for 10min.
(3) And immediately adjusting the composition of the chlorinating agent after the first-stage roasting, entering into a second-stage roasting, wherein the molar ratio of chlorine to gaseous ferric trichloride in the second-stage roasting process is 8, the molar ratio of the chlorine in the chlorinating agent to the iron in the ferronickel alloy is 9:1, and roasting at 600 ℃ for 70min to obtain second-stage roasting slag and gas.
(4) And (3) carrying out sectional condensation on the roasting gas obtained in the step (3), wherein the first-stage condensation temperature is controlled to be 150 ℃, so as to obtain solid ferric chloride, and the second-stage condensation temperature is controlled to be 25 ℃, so as to obtain silicon tetrachloride. The solid ferric chloride obtained by the first-stage condensation is subjected to component analysis, the result shows that the purity of the ferric chloride is 99.4%, and the result shows that the purity of the silicon tetrachloride obtained by the second-stage condensation is 97.5%.
(5) Ball milling is carried out on the second-stage roasting slag, ball milling media are steel balls, ball milling is carried out for 3min, nickel-rich powder is obtained, and chemical component analysis is carried out on the nickel-rich powder, so that the result shows that the volatilization rate of iron is 93.7%, and the volatilization rate of nickel is 0%.
Example 2:
the invention relates to a method for separating ferronickel by chloridizing roasting of ferronickel alloy, which has the process flow shown in figure 1 and comprises the following steps:
(1) The ferronickel alloy iron particles with the granularity of 1-2 cm are naturally piled up and arranged in a roasting furnace, and then argon is introduced to exhaust the air in the furnace.
(2) Introducing a chlorinating agent into the roasting furnace for one-stage roasting, wherein the chlorinating agent is chlorine and gaseous ferric trichloride, the molar ratio of the chlorine to the gaseous ferric trichloride is 0.2, the molar ratio of the chlorine in the chlorinating agent to the iron in the ferronickel alloy is 1:6, and the one-stage roasting temperature is controlled to be 680 ℃ and the roasting is performed for 8min.
(3) After the first-stage roasting is finished, immediately adjusting the composition of a chlorinating agent, entering into a second-stage roasting, wherein the molar ratio of chlorine to gaseous ferric trichloride in the second-stage roasting process is 12, the molar ratio of the chlorine in the chlorinating agent to the iron in the ferronickel alloy is 20:1, and roasting at 680 ℃ for 70min to obtain second-stage roasting slag and gas.
(4) And (3) carrying out sectional condensation on the roasting gas obtained in the step (3), wherein the first-stage condensation temperature is controlled to be 100 ℃, so as to obtain solid ferric chloride, and the second-stage condensation temperature is controlled to be 25 ℃, so as to obtain silicon tetrachloride. The solid ferric chloride obtained by the first-stage condensation is subjected to component analysis, the result shows that the purity of the ferric chloride is 98.2%, and the silicon tetrachloride obtained by the second-stage condensation is subjected to component analysis, and the result shows that the purity of the silicon tetrachloride is 97.7%.
(5) Ball milling the second-stage roasting slag with steel balls as ball milling medium for 3min to obtain nickel-rich powder, and analyzing the phase and chemical components of the nickel-rich powder, wherein the phase analysis is shown in figure 2, and the result shows that the main phases of the nickel-rich powder are Ni and N 3 Fe. And FeCl 3 (iron chloride is hydrate and mainly caused by the absorption of moisture in the air in the detection process), and chemical component analysis shows that the volatilization rate of iron is 94.9% and the volatilization rate of nickel is 0%.
Example 3:
the invention relates to a method for separating ferronickel by chloridizing roasting of ferronickel alloy, which has the process flow shown in figure 1 and comprises the following steps:
(1) The ferronickel alloy iron particles with the granularity of 1-2 cm are naturally piled up and arranged in a roasting furnace, and then argon is introduced to exhaust the air in the furnace.
(2) Introducing a chlorinating agent into the roasting furnace for one-stage roasting, wherein the chlorinating agent is chlorine and gaseous ferric trichloride, the molar ratio of the chlorine to the gaseous ferric trichloride is 0.4, the molar ratio of the chlorine in the chlorinating agent to the iron in the ferronickel alloy is 1:8, and the one-stage roasting temperature is controlled to be 650 ℃ and the roasting is carried out for 5min.
(3) And immediately adjusting the composition of the chlorinating agent after the first-stage roasting, entering into a second-stage roasting, wherein the molar ratio of chlorine to gaseous ferric trichloride in the second-stage roasting process is 8, the molar ratio of the chlorine in the chlorinating agent to the iron in the ferronickel alloy is 55:1, and roasting at the temperature of 650 ℃ for 150min to obtain second-stage roasting slag and gas.
(4) And (3) carrying out sectional condensation on the roasting gas obtained in the step (3), wherein the first-stage condensation temperature is controlled to be 100 ℃, so as to obtain solid ferric chloride, and the second-stage condensation temperature is controlled to be 25 ℃, so as to obtain silicon tetrachloride. The solid ferric chloride obtained by the first-stage condensation is subjected to component analysis, the result shows that the purity of the ferric chloride is 99.1 percent, and the result shows that the purity of the silicon tetrachloride obtained by the second-stage condensation is 97.2 percent.
(5) Ball milling is carried out on the second-stage roasting slag, the ball milling medium is steel balls, ball milling is carried out for 3min, the nickel-rich powder is obtained, the phase analysis is shown in figure 3, and the result shows that the main phases of the nickel-rich powder are Ni and Ni 3 Fe、FeCl 2 、FeCl 3 (the chloride of iron is hydrate and mainly caused by the absorption of moisture in the air in the detection process), and the chemical composition shows that the volatilization rate of iron is 98.3 percent and the volatilization rate of nickel is 0 percent.
Comparative example 1:
the chloridizing roasting method of the ferronickel alloy in the comparative example comprises the following steps:
(1) And naturally stacking ferronickel alloy iron particles with the granularity of 1-2 cm in a roasting furnace, and then exhausting air in the furnace by introducing argon, and respectively carrying out 3 groups of independent experiments.
(2) Introducing chlorine into a roasting furnace for roasting, wherein the roasting temperature is 600 ℃, the roasting time is 80min, the addition amounts of the chlorine gas are the same except for the addition amounts of the chlorine gas in 3 groups of independent experiments, and the addition amounts of the chlorine gas in 3 independent experiments are respectively as follows: the molar ratio of the chlorine in the chlorine to the iron in the ferronickel alloy is 3:1 (a), 10:1 (b) and 25:1 (c).
(3) After the roasting experiment is finished, the roasting slag is taken for phase and chemical composition analysis, and the phase analysis results are shown in fig. 4, 5 and 6. The results show that NiCl was present in all 3 experiments of this comparative example 2 The generation of the nickel-iron alloy by roasting the chlorine shows that the nickel is easy to volatilize and lose when the iron is chloridized, the nickel is chloridized at the same time, and most of the nickel in the slag is converted into nickel chloride. The main reason is that the chlorine is adopted to directly chloridize and bake the nickel-iron alloy, and the chloridize reaction is too severe and the reaction is exothermic, so that local high temperature is caused, and the chloridization and volatilization of nickel are caused. Chemical composition analysis shows that the volatilization rates of 3 groups of independent experiments are 62.4 percent (a), 86.7 percent (b) and 95.7 percent (c), and the volatilization rates of nickel are 3.9 percent (a), 6.4 percent (b) and 16.5 percent (c).
Claims (9)
1. The method for separating ferronickel by chloridizing roasting of the ferronickel alloy is characterized by comprising the following steps of:
(1) Placing the nickel-iron alloy into a roasting furnace;
(2) Introducing a gaseous chlorinating agent into a roasting furnace for sectional roasting to obtain roasting slag and a roasting gas phase; wherein the gaseous chlorinating agent is a mixture of chlorine and gaseous ferric chloride;
(3) And (3) carrying out sectional condensation on the roasting gas phase obtained in the step (2) to obtain solid ferric chloride and liquid silicon tetrachloride respectively.
2. The method for separating ferronickel by chloridizing roasting of ferronickel alloy according to claim 1, wherein in the step (2), the sectional roasting is divided into two sections of roasting, wherein the roasting temperature of one section of roasting is 550-690 ℃, and the roasting time is 5-15 min; the roasting temperature of the second-stage roasting is 550-750 ℃ and the roasting time is 30-180 min.
3. The method for separating ferronickel by chloridizing roasting of ferronickel alloy according to claim 2, wherein in the step (2), the molar ratio of the chlorine in the gaseous chlorinating agent to the iron in the ferronickel alloy is 1:5-1:10 in the one-stage roasting process.
4. The method for separating ferronickel by chloridizing roasting of ferronickel alloy according to claim 2, wherein in the step (2), the molar ratio of the chlorine in the gaseous chlorinating agent to the iron in the ferronickel alloy is 3:1-60:1 in the two-stage roasting process.
5. The method for separating ferronickel by chloridizing roasting of ferronickel alloy according to claim 2, wherein in the step (2), the mole ratio of chlorine in the gaseous chlorinating agent to gaseous ferric chloride in the one-stage roasting process is not higher than 0.5.
6. The method for separating ferronickel by chloridizing roasting of ferronickel alloy according to claim 2, wherein in the step (2), the molar ratio of chlorine in the gaseous chlorinating agent to gaseous ferric chloride is 8-15 in the two-stage roasting process.
7. The method for separating ferronickel by chloridizing roasting in any one of claims 1 to 6, wherein in step (3), the sectional condensation means that the roasting gas phase is first subjected to first-stage condensation at 80 to 260 ℃ and then to second-stage condensation at 25 to 30 ℃.
8. The method for separating nickel and iron by chloridizing roasting of nickel-iron alloy according to any one of claims 1-6, wherein the roasting slag obtained in the step (2) is ball-milled to obtain nickel-rich powder.
9. The method for separating ferronickel by chloridizing roasting of ferronickel alloy according to any one of claims 1 to 6, wherein the granularity of the ferronickel alloy in the step (1) is 0.3 to 4cm.
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