CN116876036A - Method for industrially producing high-purity nickel by using crude metallic nickel as raw material by using ammonium fluoride and ammonium chloride mixed solution - Google Patents
Method for industrially producing high-purity nickel by using crude metallic nickel as raw material by using ammonium fluoride and ammonium chloride mixed solution Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 212
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 100
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 53
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011259 mixed solution Substances 0.000 title claims abstract description 38
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 64
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000004090 dissolution Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000010413 mother solution Substances 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for industrially producing high-purity nickel by using crude metallic nickel as a raw material by using a mixed solution of ammonium fluoride and ammonium chloride, belonging to the technical field of metal metallurgy. Mixing crude metal nickel with a mixed solution of ammonium chloride and ammonium fluoride, introducing chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separating out nickel fluoride crystals, and cooling to continuously separate out ammonium chloride crystals to obtain mixed crystal slurry of nickel fluoride and ammonium chloride; centrifugally separating the nickel fluoride and ammonium chloride mixed crystal slurry to obtain pure nickel fluoride and ammonium chloride mixed crystals and mother liquor; dissolving the pure mixed crystal of nickel fluoride and ammonium chloride into cathode tail liquid of diaphragm electrolytic nickel, and filtering to obtain purified filtrate; and placing the purified filtrate in a diaphragm electrolytic tank for electrolysis to obtain high-purity nickel. The invention can produce high-purity nickel with the concentration of more than 5N from the crude metal nickel, has short process flow, stable product quality and low production cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of metal metallurgy, in particular to a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metal nickel as a raw material.
Background
The metal nickel is one of metals with wider use of nonferrous metals, is widely applied to industries such as electroplating, stainless steel nickel alloy, magnetic materials, batteries and the like, and along with the continuous progress and development of industry, the requirement on the metal nickel is larger and larger, and particularly, the requirement on the high-quality metal nickel is larger and larger. No. 1 and No. 0 refined nickel are mainly used for electroplating, common stainless steel alloy, battery industry and the like, and ultra-pure nickel with more than 5N is mainly used for manufacturing high-end functional nickel alloy, such as high-strength corrosion-resistant high-temperature-resistant special alloy and the like for turbine blades of high-thrust aircraft engines.
At present, the production of No. 1 (99.95%) and No. 0 (99.995%) metallic nickel adopts a sulfuric acid system electrolytic refining method, and the quality standard of 5N high-purity zinc cannot be broken through by one-time electrolysis due to the characteristics of the process, and the main production process of the ultra-pure nickel above 5N at present is as follows:
(1) Resin adsorption purification electrolytic method: the method is characterized in that nickel sulfate or nickel chloride solution with higher purity is firstly selectively adsorbed and resolved by resin, and then is electrolyzed, so that the method is complex in process, unstable in quality, high in electrolyte purifying difficulty, difficult to realize large-scale industrial production, and high in production cost of 20 ten thousand yuan/ton.
(2) By adopting the zone melting method, the process has reliable quality, but has low production efficiency, high energy consumption, high production cost, processing cost as high as 50 ten thousand yuan/ton and difficult realization of industrial scale production.
At present, the ultra-pure nickel with the concentration of more than 5N is high in production cost, low in productivity and high in sales price of more than 150 ten thousand yuan/ton, is unacceptable for most middle-high end manufacturing industries, and limits the market expansion of the nickel with the concentration of more than 5N. So that the ultra-pure nickel with the concentration of more than 5N is not produced on a large scale in the market at present.
Disclosure of Invention
The invention aims to provide a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and taking crude metal nickel as a raw material, which can directly produce high-purity nickel with the concentration of more than 5N from the crude metal nickel or the refined metal nickel, has the advantages of shorter process flow, stable product quality and low production cost, and is suitable for large-scale industrial production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metallic nickel as a raw material, which comprises the following steps:
mixing the crude metal nickel with a mixed solution of ammonium chloride and ammonium fluoride, introducing chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separating out nickel fluoride crystals, and then cooling to continuously separate out ammonium chloride crystals to obtain mixed crystal slurry of nickel fluoride and ammonium chloride; the temperature of the oxidation-dissolution conversion is 40-80 ℃; the anode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride;
centrifugally separating the nickel fluoride and ammonium chloride mixed crystal slurry to obtain pure nickel fluoride and ammonium chloride mixed crystals and mother liquor;
dissolving the pure mixed crystal of nickel fluoride and ammonium chloride into cathode tail liquid of diaphragm electrolytic nickel, and filtering to obtain purified filtrate; the cathode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride;
and placing the purified filtrate in a diaphragm electrolytic tank for electrolysis to obtain high-purity nickel.
Preferably, the time for the oxidative dissolution conversion is 60 to 200 minutes.
Preferably, the temperature of the cooling is 20-40 ℃, and the temperature of the cooling is lower than the temperature of the oxidative dissolution conversion.
Preferably, the concentration of ammonium chloride in the mixed solution of ammonium chloride and ammonium fluoride is 100-400 g/L, and the concentration of ammonium fluoride is 1-300 g/L.
Preferably, the concentration of nickel fluoride in the mixed crystal slurry of nickel fluoride and ammonium chloride is 50-300 g/L.
Preferably, the separation factor of the centrifuge used for the centrifugal separation is 300 to 1500.
Preferably, the pH value of the cathode tail liquid of the diaphragm electrolytic nickel is 6-8.
Preferably, the concentration of nickel ions in the purified filtrate is 20-150 g/l.
Preferably, the electrolysis process keeps the temperature of the anode chamber solution at 30-80 ℃, the concentration of nickel ions at 5-30 g/L and the pH value at 1-4;
the temperature of the cathode chamber solution is kept at 30-80 ℃ in the electrolytic process, the concentration of nickel ions is 10-60 g/L, and the pH value is 4-9;
the current density of the cathode plate is 200-600A/m 2 。
Preferably, the mother liquor is purified and returned to the oxidation-dissolution conversion; the purifying includes: and (3) regulating the pH value of the mother solution to 5-8 by using ammonium carbonate and ammonium sulfide, and then filtering to remove impurities.
The invention provides a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metallic nickel as a raw material, which comprises the following steps: mixing the crude metal nickel with a mixed solution of ammonium chloride and ammonium fluoride, introducing chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separating out nickel fluoride crystals, and then cooling to continuously separate out ammonium chloride crystals to obtain mixed crystal slurry of nickel fluoride and ammonium chloride; the temperature of the oxidation-dissolution conversion is 40-80 ℃; the anode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride; centrifugally separating the nickel fluoride and ammonium chloride mixed crystal slurry to obtain pure nickel fluoride and ammonium chloride mixed crystals and mother liquor; dissolving the pure mixed crystal of nickel fluoride and ammonium chloride into cathode tail liquid of diaphragm electrolytic nickel, and filtering to obtain purified filtrate; the cathode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride; and placing the purified filtrate in a diaphragm electrolytic tank for electrolysis to obtain high-purity nickel. The method can directly produce the high-purity nickel with the concentration of more than 5N (99.999-99.999999%) from the crude metal nickel, has shorter process flow, stable product quality and low production cost (not higher than 10000 yuan/ton), and is suitable for large-scale industrial production.
In addition, the invention has the characteristics of wide raw material sources, simpler process flow, easy control, low power consumption, low energy consumption, environment friendliness and no wastewater discharge.
Drawings
FIG. 1 is a flow chart of a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metallic nickel as a raw material.
Detailed Description
The invention provides a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metallic nickel as a raw material, which comprises the following steps:
mixing the crude metal nickel with a mixed solution of ammonium chloride and ammonium fluoride, introducing chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separating out nickel fluoride crystals, and then cooling to continuously separate out ammonium chloride crystals to obtain mixed crystal slurry of nickel fluoride and ammonium chloride; the temperature of the oxidation-dissolution conversion is 40-80 ℃; the anode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride;
centrifugally separating the nickel fluoride and ammonium chloride mixed crystal slurry to obtain pure nickel fluoride and ammonium chloride mixed crystals and mother liquor;
dissolving the pure mixed crystal of nickel fluoride and ammonium chloride into cathode tail liquid of diaphragm electrolytic nickel, and filtering to obtain purified filtrate; the cathode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride;
and placing the purified filtrate in a diaphragm electrolytic tank for electrolysis to obtain high-purity nickel.
The invention mixes the crude metal nickel with the mixed solution of ammonium chloride and ammonium fluoride, introduces chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separates out nickel fluoride crystal, then cools and continues to separate out ammonium chloride crystal, and obtains the mixed crystal slurry of nickel fluoride and ammonium chloride.
In the present invention, the purity of the crude metallic nickel is preferably 90 to 99.995%.
In the present invention, the mixed solution of ammonium chloride and ammonium fluoride is preferably obtained by dissolving ammonium chloride and ammonium fluoride in water. In the present invention, the concentration of ammonium chloride in the mixed solution of ammonium chloride and ammonium fluoride is preferably 100 to 400 g/l, more preferably 150 to 250 g/l; the concentration of ammonium fluoride is preferably 1 to 300 g/l, more preferably 5 to 250 g/l, still more preferably 5 to 150 g/l. In the invention, the mass ratio of the crude metallic nickel to the mixed solution of ammonium chloride and ammonium fluoride is preferably 1: (5-100), more preferably (5-50), still more preferably (1) (10-20).
In the invention, the anode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride; the concentration of each component in the anode tail liquid of the diaphragm electrolytic nickel is not particularly limited, and the anode tail liquid of the diaphragm electrolytic nickel well known in the art can be used. In the present invention, the pH value of the anode tail liquid of the diaphragm electrolytic nickel is preferably 1 to 4, and in the present invention, the anode tail liquid of the diaphragm electrolytic nickel is preferably used in such an amount that the pH value of the oxidative dissolution conversion system is preferably 2 to 5. In the invention, the anode tail liquid is used for providing ammonium chloride and ammonium fluoride required by nickel dissolution, so that the ammonium chloride and the ammonium fluoride can be recycled in a process system.
The invention has no special requirement on the dosage of the chlorine gas, and can oxidize the metallic nickel into divalent nickel.
In the invention, preferably, crude metallic nickel is put into a dissolution reaction tank of a mixed solution of ammonium fluoride and ammonium chloride, then chlorine and anode tail liquid of diaphragm electrolysis nickel are introduced, and the dissolution liquid is stirred until the metallic nickel is completely oxidized and dissolved and is converted into nickel fluoride crystals.
In the present invention, the temperature of the oxidative dissolution transition is preferably 40 to 80 ℃, more preferably 50 to 70 ℃; the time for the oxidative dissolution transition is preferably 60 to 200 minutes, more preferably 100 to 160 minutes.
In the present invention, the temperature of the cooling is preferably 20 to 40 ℃, and the temperature of the cooling is lower than the temperature of the oxidative dissolution transition. In the cooling process, ammonium chloride crystals are separated out under the condition that the pH value is 2-5, and the mixed crystal slurry of nickel fluoride and ammonium chloride is obtained. In the present invention, the concentration of nickel fluoride in the mixed crystal slurry of nickel fluoride and ammonium chloride is preferably 50 to 300 g/l.
After the mixed crystal slurry of nickel fluoride and ammonium chloride is obtained, the mixed crystal slurry of nickel fluoride and ammonium chloride is centrifugally separated to obtain pure mixed crystal of nickel fluoride and ammonium chloride and mother liquor.
In the present invention, the separation factor of the centrifuge used for the centrifugal separation is preferably 300 to 1500, more preferably 500 to 1200, and still more preferably 700 to 1000. The invention uses centrifugal separation to separate the impurity dissolved in the mother liquor from the mixed crystal of zinc fluoride and ammonium chloride, thus achieving the purification effect.
In the present invention, the mother liquor is preferably purified and returned to the oxidative dissolution conversion step; the purification preferably comprises: and (3) regulating the pH value of the mother solution to 5-8 by using ammonium carbonate and ammonium sulfide, and then filtering to remove impurities. The pH value of the mother solution is adjusted to 5-8, and metal ion impurities in the mother solution are removed in the form of solid metal sulfide or insoluble carbonate.
After pure mixed crystals of nickel fluoride and ammonium chloride are obtained, the pure mixed crystals of nickel fluoride and ammonium chloride are dissolved into cathode tail liquid of diaphragm electrolytic nickel, and the purified filtrate is obtained by filtering.
In the invention, the cathode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride. The invention has no special requirement on the concentration of each substance in the cathode tail liquid of the diaphragm electrolytic nickel, and the cathode tail liquid of the diaphragm electrolytic nickel which is well known in the field can be used. The invention has no special requirement on the dosage of cathode tail liquid of diaphragm electrolytic nickel, and can completely dissolve pure mixed crystal of nickel fluoride and ammonium chloride. In the present invention, the temperature of the dissolution is preferably 10 to 100 ℃, more preferably 20 to 80 ℃, still more preferably 40 to 60 ℃.
In the present invention, the pH of the cathode tail solution of the diaphragm electrolytic nickel is preferably 6 to 8, more preferably 6.5 to 7.5. When the pH value of the cathode tail liquid of the diaphragm electrolytic nickel does not meet the requirement, the pH value of the cathode tail liquid of the diaphragm electrolytic nickel is preferably adjusted to be in the range by adopting ammonia water. The invention removes insoluble impurities mixed in the mixed crystal of nickel fluoride and ammonium chloride by re-dissolving the mixed crystal of nickel fluoride and ammonium chloride.
In the present invention, the filtration is preferably a filter press filtration. In the present invention, the concentration of nickel ions in the purification filtrate is preferably 20 to 150 g/l, more preferably 50 to 120 g/l, and still more preferably 70 to 100 g/l.
After the purified filtrate is obtained, the purified filtrate is placed in a diaphragm electrolytic tank for electrolysis, and high-purity nickel is obtained.
In the invention, the electrolysis process preferably keeps the temperature of the anode chamber solution at 30-80 ℃, the concentration of nickel ions at 5-30 g/L and the pH value at 1-4; more preferably, the temperature of the anode chamber solution is 40-70 ℃, the nickel ion concentration is 10-25 g/L, and the pH value is 2-4.
In the invention, the temperature of the cathode chamber solution is preferably kept at 30-80 ℃, the nickel ion concentration is 10-60 g/L, and the pH value is 4-9 in the electrolysis process; more preferably, the temperature of the cathode chamber solution is 40-70 ℃, the nickel ion concentration is 20-50 g/L, and the pH value is 5-8.
In the present invention, the cathode plate current density is preferably 200 to 600A/m 2 More preferably 300 to 500A/m 2 Further preferably 350 to 450A/m 2 。
In the present invention, the electrolysis time is preferably 6 to 96 hours, more preferably 10 to 90 hours, and still more preferably 20 to 80 hours.
In the invention, the purifying filtrate enters an electrolytic catholyte circulation tank, then enters a cathode chamber of a diaphragm electrolytic tank, permeates into an anode chamber from the cathode chamber through a diaphragm to form anolyte, and obtains a high-purity electrolytic nickel plate on a cathode plate of the cathode chamber. The concentration of the nickel in the purifying liquid is higher, metal nickel is precipitated in the cathode chamber of the electrolytic tank after the purifying liquid is added into the electrolytic solution, the concentration of nickel ions in the electrolytic solution is reduced, and the purifying liquid with higher nickel concentration is required to be continuously supplemented to keep the concentration of the nickel in the electrolytic solution stable. The tail liquid generated by the anode and the mixed gas containing chlorine gas are collected and conveyed to an oxidation-dissolution conversion process to be used as an oxidant. The tail liquid generated by the cathode is used for dissolving pure nickel fluoride and ammonium chloride mixed crystals.
FIG. 1 is a flow chart of a method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metallic nickel as a raw material.
As shown in figure 1, the invention mixes crude metal nickel with mixed solution of ammonium chloride and ammonium fluoride, introduces chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separates out nickel fluoride crystal, then cools and continues to separate out ammonium chloride crystal, and obtains mixed crystal slurry of nickel fluoride and ammonium chloride; centrifugally separating the nickel fluoride and ammonium chloride mixed crystal slurry to obtain pure nickel fluoride and ammonium chloride mixed crystals and mother liquor; the mother liquor is preferably purified and returned to the oxidation-dissolution conversion process; dissolving the pure mixed crystal of nickel fluoride and ammonium chloride into cathode tail liquid of diaphragm electrolytic nickel, and filtering to obtain purified filtrate; and placing the purified filtrate in a diaphragm electrolytic tank for electrolysis to obtain high-purity nickel. The tail liquid generated by the anode and the mixed gas containing chlorine gas are collected and conveyed to an oxidation dissolving process to be used as an oxidant. The tail liquid generated by the cathode is used for dissolving pure nickel fluoride and ammonium chloride mixed crystals.
The method for industrially producing high-purity nickel from crude metallic nickel using a mixed solution of ammonium fluoride and ammonium chloride according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Step 1): oxidation, dissolution, conversion and purification procedures: 100kg of raw material of crushed metallic nickel particles (purity 99.95%) were charged to a bed of 2m 3 In a dissolution reaction tank of a mixed solution of diaphragm electrolysis anode tail liquid, ammonium chloride and ammonium fluoride, the mass ratio of metallic nickel to the mixed solution is 1:20, and the mixed solution of ammonium chloride and ammonium fluoride is prepared by the steps ofThe concentration of ammonium chloride was 350 g/l and the concentration of ammonium fluoride was 75 g/l. 120 kg of chlorine (tail gas of an electrolytic nickel anode) is added in the process of dissolving metallic nickel, the dissolved solution is stirred until the metallic nickel is completely oxidized and dissolved and is converted into nickel fluoride crystals, the pH value is kept at 4.5 in the process of reaction by controlling the adding amount of tail liquid (pH value is 2) of the electrolytic nickel anode through a tail liquid diaphragm, the reaction temperature is 80 ℃, and the dissolution reaction time is 180 minutes. After the reaction, the solution is cooled to 35 ℃ to crystallize and separate out ammonium chloride, and then the slurry is led into a process of separating and purifying the mixed crystal of nickel fluoride and ammonium chloride.
Step 2): separating and purifying nickel fluoride and ammonium chloride mixed crystals: introducing the slurry obtained in the step 1) into a centrifugal machine, wherein the separation factor of the centrifugal machine is 1200; the impurities dissolved in the mother liquor are separated from the mixed crystal of nickel fluoride and ammonium chloride, so as to achieve the purification effect. After separation and purification are finished, the mother liquor enters a mother liquor purification procedure; the obtained pure mixed crystal powder crystal of nickel fluoride and ammonium chloride is put into a nickel fluoride dissolving and purifying process.
Step 3): purifying nickel fluoride crystallization mother liquor: adding ammonium carbonate and ammonium sulfide into the mother solution to make the pH value of the solution be 7, precipitating and filtering other metal impurities and nickel in the mother solution, and returning the filtrate to the oxidation and dissolution conversion process.
Step 4): nickel fluoride dissolution and purification: the mixed crystal powder crystal of nickel fluoride and ammonium chloride obtained in the step 2) is put into a reactor filled with 2m 3 In a stirring reaction tank for diaphragm electrolysis of nickel catholyte (300 g/L of ammonium chloride, 45 g/L of nickel ions, 80 g/L of ammonium fluoride and 0.6 mol/L of ammonia), 50kg of ammonia water with the mass concentration of 20% is added, stirring is started for 60 minutes, a proper amount of ammonia water is added to completely dissolve nickel fluoride and ammonium chloride, and the solution is filtered by a filter press to obtain purified filtrate and filter residues. The concentration of nickel ions in the purified filtrate is 90 g/L; the filter residue is discarded as impurities, and the purified filtrate is led into an electrolysis process.
Step 5): and (3) an electrolysis procedure: the electrolytic tank of the process adopts an anion diaphragm electrolytic tank, and the purified filtrate obtained in the step (4) is slowly led into an electrolytic catholyte circulation tank, so that the concentration of nickel ions in the electrolytic catholyte is 45 g/L; the free ammonia concentration was 0.6 mol/l; and (3) after power is applied, an ultrapure electrolytic nickel plate is obtained on the titanium cathode plate, chlorine is obtained at the anode, the chlorine is collected and then is guided to be used in the step (1), and after electrolysis is carried out for 48 hours, the cathode is taken out, so that the ultrapure nickel plate with the purity of 99.9999% can be obtained.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for industrially producing high-purity nickel by using a mixed solution of ammonium fluoride and ammonium chloride and using crude metallic nickel as a raw material comprises the following steps:
mixing the crude metal nickel with a mixed solution of ammonium chloride and ammonium fluoride, introducing chlorine and anode tail liquid of diaphragm electrolytic nickel to perform oxidation, dissolution and conversion, separating out nickel fluoride crystals, and then cooling to continuously separate out ammonium chloride crystals to obtain mixed crystal slurry of nickel fluoride and ammonium chloride; the temperature of the oxidation-dissolution conversion is 40-80 ℃; the anode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride;
centrifugally separating the nickel fluoride and ammonium chloride mixed crystal slurry to obtain pure nickel fluoride and ammonium chloride mixed crystals and mother liquor;
dissolving the pure mixed crystal of nickel fluoride and ammonium chloride into cathode tail liquid of diaphragm electrolytic nickel, and filtering to obtain purified filtrate; the cathode tail liquid of the diaphragm electrolytic nickel is a mixed solution containing ammonium fluoride, ammonium chloride and nickel chloride;
and placing the purified filtrate in a diaphragm electrolytic tank for electrolysis to obtain high-purity nickel.
2. The method of claim 1, wherein the oxidative dissolution transition time is 60 to 200 minutes.
3. The method of claim 1, wherein the cooled temperature is 20-40 ℃, and the cooled temperature is below the temperature of oxidative dissolution transition.
4. The method according to claim 1, wherein the concentration of ammonium chloride in the mixed solution of ammonium chloride and ammonium fluoride is 100 to 400 g/l and the concentration of ammonium fluoride is 1 to 300 g/l.
5. The method according to claim 1, wherein the concentration of nickel fluoride in the mixed crystal slurry of nickel fluoride and ammonium chloride is 50 to 300 g/l.
6. The method according to claim 1, wherein the separation factor of the centrifuge used for the centrifugal separation is 300 to 1500.
7. The method of claim 1, wherein the pH of the cathode tail of the diaphragm electrolytic nickel is between 6 and 8.
8. The method according to claim 1, wherein the concentration of nickel ions in the purge filtrate is 20 to 150 g/l.
9. The method according to claim 1, wherein the electrolysis process maintains the anode compartment solution temperature at 30-80 ℃, the nickel ion concentration at 5-30 g/l, and the pH at 1-4;
the temperature of the cathode chamber solution is kept at 30-80 ℃ in the electrolytic process, the concentration of nickel ions is 10-60 g/L, and the pH value is 4-9;
the current density of the cathode plate is 200-600A/m 2 。
10. The method according to claim 1, wherein the mother liquor is purified and returned to the oxidative dissolution shift; the purifying includes: and (3) regulating the pH value of the mother solution to 5-8 by using ammonium carbonate and ammonium sulfide, and then filtering to remove impurities.
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