CN112359226A - Method for preparing high-purity nickel - Google Patents
Method for preparing high-purity nickel Download PDFInfo
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- CN112359226A CN112359226A CN202011060964.7A CN202011060964A CN112359226A CN 112359226 A CN112359226 A CN 112359226A CN 202011060964 A CN202011060964 A CN 202011060964A CN 112359226 A CN112359226 A CN 112359226A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 14
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 17
- 238000004090 dissolution Methods 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000007306 turnover Effects 0.000 claims description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910018100 Ni-Sn Inorganic materials 0.000 description 1
- 229910018532 Ni—Sn Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- -1 radioactive elements Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- 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
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/06—Refining
- C22B23/065—Refining carbonyl methods
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for preparing high-purity nickel, which adopts a high-temperature negative pressure method to mix nickel sulfide ore particles and nickel sulfide ore particles to realize primary reduction and desulfurization to prepare a crude nickel simple substance, and the crude nickel simple substance is introduced into carbon monoxide to release heat to obtain Ni (CO)4Then heating Ni (CO)4The nickel is further refined, the refined nickel is placed in a hydrochloric acid environment with the pH value of 1-3, and chlorine is introduced at the same time, so that high-purity NiCl is prepared2The solution is then purified by deoiling and anion exchange resin exchange, and finally the high-purity nickel simple substance is obtained by electrodeposition, the invention has the advantages that the redox flow is introduced on the basis of the traditional liquid-phase electrolytic electrodeposition preparation of the nickel simple substance,can effectively remove anions doped in the nickel simple substance, thereby obtaining the nickel simple substance with higher purity.
Description
Technical Field
The invention relates to the field of metal production and processing, in particular to a method for preparing high-purity nickel.
Background
Further development of high-tech technologies requires the provision of sufficient specialty materials, and various metals have been found to serve as strategic materials for high-tech technologies and require purification to very high purity. The preparation, characterization and application of high purity, ultra-high purity metals in the modern material science and engineering fields are novel, viable and growing fields. High-purity metals of more than 5N are widely applied to the production of semiconductor elements and very large scale integrated elements. The production of electronic devices and printed circuit boards requires about 20 kinds of high-purity metals, such as gallium, indium, arsenic, antimony, cadmium, lead, tin, tellurium, bismuth, sulfur, zinc, copper, selenium, phosphorus, and their compounds and alloy materials.
Nickel is commonly used in the fields of conventional stainless steels, alloys, etc. The demand for high purity nickel has increased in particular areas in recent years. For example, superalloys made from high purity nickel are used in the manufacture of aircraft engines, in nuclear reactor protection materials, in biomaterials, in low expansion alloys; high purity nickel is also growing for the electronics industry, for example one special nickel-iron alloy is widely used for lead frames, another Cu-Ni-Sn alloy is used for wiring ports; high purity nickel is also used in hydrogenation catalysts and other chemicals. When high-purity nickel is used for large-scale integrated circuits and wiring materials thereof, magnetic films, and special packaging materials, it is required that the content of impurities such as alkali metals, radioactive elements, transition metal elements, and gas elements is very low.
In the existing production method of high-purity nickel, in order to solve the problem of high acid of the electro-dissolution stock solution, the method of boiling to remove acid and neutralizing to reduce acid is adopted, so that the production cost is high, and the pollution is easy to generate; the deep purification of the solution is not ideal. The soluble anode is adopted, so that mutual pollution of an electrolytic cathode and an anolyte is easy to occur, and the impurity content of high-purity nickel is high.
Chinese patent with application number CN200410070648.2 discloses a method for preparing high-purity nickel, relating to a method for preparing high-purity nickel by electrodeposition of hydrochloric acid solution system, which is characterized in that the process comprises the following steps: the method comprises the steps of preparing NiCl2 solution with pH of 1-3 by electro-dissolution by using a hydrochloric acid system and 3N electrolytic nickel as an anode, performing three-stage countercurrent extraction on the electro-dissolved solution by using an anion extractant, deoiling the solution after the back extraction, sequentially introducing anion exchange resin for ion exchange deep purification, and finally introducing the solution into an electrolytic cell for electrodeposition, wherein the amount of the solution subjected to the introduced ion exchange purification is equal to that of the solution after the extracted electrodeposition, and obtaining high-purity nickel by electrodeposition.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for preparing high-purity nickel aiming at the defects of the prior art.
The technical scheme is as follows: the invention relates to a method for preparing high-purity nickel, which comprises the following steps:
s1, taking 2 parts of industrial sulfide ore with 0.3-0.5% nickel, and grinding to 100 meshes;
s2, taking 1 part of oxide ore with the industrial grade of 0.3-0.5% nickel, and grinding to 100 meshes;
s3, mixing the crushed nickel sulfide ore particles of S1 and S2 with the crushed nickel sulfide ore particles, and adding the mixture at 1000 ℃ and 10 ℃-2Fully reacting in a sealed reaction kettle under the negative pressure of mmHg for 45min to obtain a crude nickel simple substance;
s4, putting the crude nickel simple substance prepared in the S3 into a turnover high-pressure reaction kettle, continuously introducing carbon monoxide for 36min, reducing the temperature to-10 to-5 ℃, fully reacting to generate nickel tetracarbonyl, continuously heating the nickel tetracarbonyl to 117 ℃, keeping the temperature for 15min, and further refining the crude nickel simple substance;
s5, putting the product in the S4 into a hydrochloric acid system with the pH of 1-3, stirring at the rotating speed of 120-150 r/min, and introducing chlorine gas to continuously perform a reduction reaction;
s6, performing back extraction on the product in the S5, and introducing into an activated carbon column for deoiling treatment;
s7, introducing the reaction product in the S6 into anion exchange resin for exchange purification;
s8, putting the product purified in the S7 into an electrolytic cell for electrodeposition, wherein the pH value of an electrodeposition solution is 1-3, the temperature of an electrodeposition environment is 50 ℃, and the current density is 100-200A/m2Continuously pumping the solution after electrodeposition in the electrodeposition reaction process, and internally circulating the solution in the electrodeposition tank to obtain the high-purity nickel by electrodeposition.
The method for preparing high-purity nickel according to claim 1, wherein: and (3) introducing chlorine into the S5 by adopting an intermittent bubbling method, and introducing chlorine into the S5 for reduction reaction at an interval bubbling method of opening a valve for 30S and closing the valve for 30S under the pressure of 2MPa and the flow rate of 0.2-0.5L/min.
Preferably, the anion exchange resin used in S7 comprises a wet anion exchange resin.
Preferably, the wet anion exchange resins employed in S7 include 201 × 7 strongly basic type I anion exchange resins, D201 macroporous anion exchange resins, and 717 wet anion exchange resins.
Preferably, in the exchange purification process in S7, the reaction vessel is kept vibrating at a frequency of 13000Hz, and the exchange flow rate is controlled to be less than or equal to 2 Bu/h.
Preferably, the temperature is lowered to-10 ℃ while carbon monoxide is passed into S4.
Preferably, the S5 is introduced with chlorine gas to carry out reduction reaction and simultaneously carry out the electro-dissolution reaction to prepare high-purity NiCl2And (3) solution.
Preferably, the current density during the electro-dissolution reaction in S5 is 100-200A/m2When the hydrogen ion concentration is reduced to 1 g/L-2 g/L in the last stage of liquid making, the current density is 30-70A/m2。
Compared with the prior art, the invention has the following beneficial effects: (1) an oxidation-reduction process is introduced on the basis of preparing the nickel simple substance by the traditional liquid-phase electrolytic electrodeposition, so that anions doped in the nickel simple substance can be effectively removed, and the nickel simple substance with higher purity can be obtained;
(2) in S4, nickel can be effectively separated from other metal ions, so that the purity of the nickel prepared in advance can be greatly improved to be higher and reach the standard of more than 3N before the preparation process enters the liquid phase reaction and electrodeposition process, and a nickel simple substance with the purity higher than 5N nickel can be obtained after the subsequent exchange purification and electrodeposition process, and even can reach 6N nickel.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, unless otherwise specifically stated or limited, the terms "mounted," "connected," "fixed," and the like are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally formed; the connection can be mechanical connection, electrical connection or communication connection; either directly or indirectly through intervening media, either internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The technical solution of the present invention will be described in detail below with specific examples. The following several specific embodiments may be combined with each other, and details of the same or similar concepts or processes may not be repeated in some embodiments.
Example 1: a method for preparing high-purity nickel, comprising the following steps:
s1, taking 2 parts of industrial sulfide ore with 0.3-0.5% nickel, and grinding to 100 meshes;
s2, taking 1 part of oxide ore with the industrial grade of 0.3-0.5% nickel, and grinding to 100 meshes;
s3, mixing the crushed nickel sulfide ore particles of S1 and S2 with the crushed nickel sulfide ore particles, and adding the mixture at 1000 ℃ and 10 ℃-2Fully reacting in a sealed reaction kettle under the negative pressure of mmHg for 45min to obtain a crude nickel simple substance;
s4, putting the crude nickel simple substance prepared in the S3 into a turnover high-pressure reaction kettle, continuously introducing carbon monoxide for 36min, reducing the temperature to-7 ℃, fully reacting to generate nickel tetracarbonyl, continuously heating the nickel tetracarbonyl to 117 ℃, keeping the temperature for 15min, and further refining the crude nickel simple substance;
s5, putting the product in the S4 into a hydrochloric acid system with pH2, stirring at the rotating speed of 130r/min, and introducing chlorine gas to continuously perform a reduction reaction;
s6, performing back extraction on the product in the S5, and introducing into an activated carbon column for deoiling treatment;
s7, introducing the reaction product in the S6 into anion exchange resin for exchange purification;
s8, putting the product purified in S7 into an electrolytic cell for electrodeposition, wherein the pH value of an electrodeposition solution is 2, the temperature of an electrodeposition environment is 50 ℃, and the current density is 150A/m2Continuously pumping the solution after electrodeposition in the electrodeposition reaction process, and internally circulating the solution in the electrodeposition tank to obtain the high-purity nickel by electrodeposition.
Example 2: a method for preparing high-purity nickel, comprising the following steps:
s1, taking 2 parts of industrial sulfide ore with 0.3-0.5% nickel, and grinding to 100 meshes;
s2, taking 1 part of oxide ore with the industrial grade of 0.3-0.5% nickel, and grinding to 100 meshes;
s3, mixing the crushed nickel sulfide ore particles of S1 and S2 with the crushed nickel sulfide ore particles, and adding the mixture at 1000 ℃ and 10 ℃-2Fully reacting in a sealed reaction kettle under the negative pressure of mmHg for 45min to obtain a crude nickel simple substance;
s4, putting the crude nickel simple substance prepared in the S3 into a turnover high-pressure reaction kettle, continuously introducing carbon monoxide for 36min, reducing the temperature to-10 ℃, fully reacting to generate nickel tetracarbonyl, continuously heating the nickel tetracarbonyl to 117 ℃, keeping the temperature for 15min, and further refining the crude nickel simple substance;
s5, putting the product in S4 into a hydrochloric acid system with pH1, stirring at the rotating speed of 120r/min, introducing chlorine gas to continuously perform a reduction reaction, and performing an electro-dissolution reaction to prepare high-purity NiCl2The current density of the solution during the electro-dissolution reaction is 100A/m2When the hydrogen ion concentration is reduced to the final stage of the liquid preparation of 2g/L, the current density is 30A/m2；
S6, performing back extraction on the product in the S5, and introducing into an activated carbon column for deoiling treatment;
s7, introducing the reaction product in the S6 into anion exchange resin for exchange purification;
s8, putting the product purified in S7 into an electrolytic cell for electrodeposition, wherein the pH value of an electrodeposition solution is 11, the temperature of an electrodeposition environment is 50 ℃, and the current density is 100A/m2Continuously pumping the solution after electrodeposition in the electrodeposition reaction process, and internally circulating the solution in the electrodeposition tank to obtain the high-purity nickel by electrodeposition.
Example 3: a method for preparing high-purity nickel, comprising the following steps:
s1, taking 2 parts of industrial sulfide ore with 0.3-0.5% nickel, and grinding to 100 meshes;
s2, taking 1 part of oxide ore with the industrial grade of 0.3-0.5% nickel, and grinding to 100 meshes;
s3, mixing the crushed nickel sulfide ore particles of S1 and S2 with the crushed nickel sulfide ore particles, and adding the mixture at 1000 ℃ and 10 ℃-2Fully reacting in a sealed reaction kettle under the negative pressure of mmHg for 45min to obtain a crude nickel simple substance;
s4, putting the crude nickel simple substance prepared in the S3 into a turnover high-pressure reaction kettle, continuously introducing carbon monoxide for 36min, reducing the temperature to-10 ℃, fully reacting to generate nickel tetracarbonyl, continuously heating the nickel tetracarbonyl to 117 ℃, keeping the temperature for 15min, and further refining the crude nickel simple substance;
s5, putting the product in S4 into a hydrochloric acid system with pH3, stirring at the rotating speed of 150r/min, introducing chlorine gas to continuously perform a reduction reaction, and performing an electro-dissolution reaction to prepare high-purity NiCl2The current density of the solution during the electro-dissolution reaction is 200A/m2When the hydrogen ion concentration is reduced to the final stage of liquid making of 1g/L, the current density adopted is 30A/m2；
S6, performing back extraction on the product in the S5, and introducing into an activated carbon column for deoiling treatment;
s7, introducing the reaction product in the S6 into anion exchange resin for exchange purification;
s8, putting the purified product in S7 into an electrolytic cell for electrodeposition, wherein the pH value of an electrodeposition solution is 3, the temperature of an electrodeposition environment is 50 ℃, and the current density is 200A/m2Continuously pumping the solution after electrodeposition in the electrodeposition reaction process, and internally circulating the solution in the electrodeposition tank to obtain the high-purity nickel by electrodeposition.
Example 4: a method for preparing high-purity nickel, comprising the following steps:
s1, taking 2 parts of industrial sulfide ore with 0.3-0.5% nickel, and grinding to 100 meshes;
s2, taking 1 part of oxide ore with the industrial grade of 0.3-0.5% nickel, and grinding to 100 meshes;
s3, mixing the crushed nickel sulfide ore particles of S1 and S2 with the crushed nickel sulfide ore particles, and adding the mixture at 1000 ℃ and 10 ℃-2Fully reacting in a sealed reaction kettle under the negative pressure of mmHg for 45min to obtain a crude nickel simple substance;
s4, putting the crude nickel simple substance prepared in the S3 into a turnover high-pressure reaction kettle, continuously introducing carbon monoxide for 36min, reducing the temperature to-10 ℃, fully reacting to generate nickel tetracarbonyl, continuously heating the nickel tetracarbonyl to 117 ℃, keeping the temperature for 15min, and further refining the crude nickel simple substance;
s5, putting the product in S4 into a hydrochloric acid system with pH1, stirring at the rotating speed of 150r/min, introducing chlorine gas to continuously perform a reduction reaction, and performing an electro-dissolution reaction to prepare high-purity NiCl2The current density of the solution during the electro-dissolution reaction is 200A/m2When the hydrogen ion concentration is reduced to the final stage of liquid making of 1g/L, the current density is 70A/m2；
S6, performing back extraction on the product in the S5, and introducing into an activated carbon column for deoiling treatment;
s7, introducing the reaction product in the S6 into anion exchange resin for exchange purification;
s8, putting the purified product in S7 into an electrolytic cell for electrodeposition, wherein the pH value of an electrodeposition solution is 1, the temperature of an electrodeposition environment is 50 ℃, and the current density is 200A/m2Continuously pumping the solution after electrodeposition in the electrodeposition reaction process, and internally circulating the solution in the electrodeposition tank to obtain the high-purity nickel by electrodeposition.
The purity of the elemental nickel prepared in the examples 1, 2, 3 and 4 is respectively 99.9992%, 99.9994%, 99.9996% and 99.9998% by detection, and the experimental parameters of the comparative examples 1, 2, 3 and 4 show that the chlorine is introduced to continuously perform the reduction reaction and simultaneously perform the electric dissolution reaction in the S5 to prepare the high-purity NiCl2The solution can effectively improve the purity of the final elemental nickel product, and the lower the pH value of the hydrochloric acid environment during the electro-dissolution reaction, the higher the current density of the electro-dissolution, and the higher the purity of the generated elemental nickel.
In the present invention, unless otherwise explicitly specified or limited, the first feature "on" or "under" the second feature may be directly contacting the first feature and the second feature or indirectly contacting the first feature and the second feature through an intermediate. Also, a first feature "on," "above," and "over" a second feature may mean that the first feature is directly above or obliquely above the second feature, or that only the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lower level than the second feature. In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example" or "some examples," or the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example.
Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing high-purity nickel is characterized by comprising the following steps: the method comprises the following steps:
s1, taking 2 parts of industrial sulfide ore with 0.3-0.5% nickel, and grinding to 100 meshes;
s2, taking 1 part of oxide ore with the industrial grade of 0.3-0.5% nickel, and grinding to 100 meshes;
s3, mixing the crushed nickel sulfide ore particles of S1 and S2 with the crushed nickel sulfide ore particles, and adding the mixture at 1000 ℃ and 10 ℃-2Fully reacting in a sealed reaction kettle under the negative pressure of mmHg for 45min to obtain a crude nickel simple substance;
s4, putting the crude nickel simple substance prepared in the S3 into a turnover high-pressure reaction kettle, continuously introducing carbon monoxide for 36min, reducing the temperature to-10 to-5 ℃, fully reacting to generate nickel tetracarbonyl, continuously heating the nickel tetracarbonyl to 117 ℃, keeping the temperature for 15min, and further refining the crude nickel simple substance;
s5, putting the product in the S4 into a hydrochloric acid system with the pH of 1-3, stirring at the rotating speed of 120-150 r/min, and introducing chlorine gas to continuously perform a reduction reaction;
s6, performing back extraction on the product in the S5, and introducing into an activated carbon column for deoiling treatment;
s7, introducing the reaction product in the S6 into anion exchange resin for exchange purification;
s8, putting the product purified in the S7 into an electrolytic cell for electrodeposition, wherein the pH value of an electrodeposition solution is 1-3, the temperature of an electrodeposition environment is 50 ℃, and the current density is 100-200A/m2Continuously pumping the solution after electrodeposition in the electrodeposition reaction process, and internally circulating the solution in the electrodeposition tank to obtain the high-purity nickel by electrodeposition.
2. The method for preparing high-purity nickel according to claim 1, wherein: and (3) introducing chlorine into the S5 by adopting an intermittent bubbling method, and introducing chlorine into the S5 for reduction reaction at an interval bubbling method of opening a valve for 30S and closing the valve for 30S under the pressure of 2MPa and the flow rate of 0.2-0.5L/min.
3. The method for preparing high-purity nickel according to claim 1, wherein: the anion exchange resin used in S7 includes a wet anion exchange resin.
4. The method for preparing high-purity nickel according to claim 3, wherein: the wet anion exchange resins used in S7 include 201 × 7 strongly basic type I anion exchange resins, D201 macroporous anion exchange resins and 717 wet anion exchange resins.
5. The method for preparing high-purity nickel according to claim 1, wherein: in the exchange purification process in S7, the reaction vessel is kept vibrating at 13000Hz, and the exchange flow rate is controlled to be less than or equal to 2 Bu/h.
6. The method for preparing high-purity nickel according to claim 1, wherein: the temperature was reduced to-10 ℃ while introducing carbon monoxide into S4.
7. The method for preparing high-purity nickel according to claim 1, wherein: introducing chlorine into S5 for reduction reaction and simultaneously carrying out electric dissolution reaction to prepare high-purity NiCl2And (3) solution.
8. The method for preparing high-purity nickel according to claim 7, wherein: the current density during the electro-dissolution reaction in S5 is 100-200A/m2When the hydrogen ion concentration is reduced to 1 g/L-2 g/L in the last stage of liquid making, the current density is 30-70A/m2。
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| CN113735199A (en) * | 2021-08-25 | 2021-12-03 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate from nickel iron |
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| CN113735199A (en) * | 2021-08-25 | 2021-12-03 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate from nickel iron |
| CN113735199B (en) * | 2021-08-25 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate from nickel iron |
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