CN114192792B - Method for preparing high-purity cobalt and application thereof - Google Patents
Method for preparing high-purity cobalt and application thereof Download PDFInfo
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- CN114192792B CN114192792B CN202111439462.XA CN202111439462A CN114192792B CN 114192792 B CN114192792 B CN 114192792B CN 202111439462 A CN202111439462 A CN 202111439462A CN 114192792 B CN114192792 B CN 114192792B
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 46
- 239000010941 cobalt Substances 0.000 title claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000001868 cobalt Chemical class 0.000 claims abstract description 39
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001284 azanium sulfanide Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000005291 magnetic effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 20
- 239000000047 product Substances 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
Classifications
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- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for preparing high-purity cobalt and application thereof. The method comprises the following steps: mixing cobalt salt with a precipitator, precipitating, filtering, and concentrating the obtained filtrate to obtain high-purity cobalt salt; reducing the high-purity cobalt salt to obtain high-purity cobalt; wherein the precipitant is one or more selected from ammonium bisulfide, hydrogen sulfide, ammonia gas and ammonia water. The method can effectively remove the impurities in the cobalt salt, avoids introducing new impurities in the impurity removal process, has high purity of the prepared cobalt, low copper, nickel and iron content and excellent product quality, and has strong operability, low cost and wide application prospect.
Description
Technical Field
The invention relates to the technical field of high-purity metal materials, in particular to a method for preparing high-purity cobalt and application thereof.
Background
The high-purity cobalt (Co) has excellent ferromagnetic property and good conductive property, and has important application in the fields of atomic layer deposition precursors, integrated circuit chips, sputtering targets in the preparation process of magnetic recording media and the like.
With the reduction of line width in semiconductor processes, cobalt is used as a metal interconnect wire in processes below 5nm, and higher requirements are put on the purity of cobalt sputtering targets, and it is desirable that the purity of cobalt reaches 5N or higher, especially the content of metal impurities such as Cu, ni, fe, etc. is more severe. The high purity cobalt can also be used as a precursor (Co (CO)) for atomic layer vapor deposition in advanced semiconductor processes 3 NO，CpCo(CO) 2 ，CCTBA，(EtCp) 2 Co, coDAD, etc.), cobalt with high purity is used as a raw material, and the difficulty of purifying the metal organic compound in the later stage can be greatly reduced.
In recent years, the method is used for preparing high-purity Co by adopting the steps of purifying cobalt salt solution, electrolytic refining and smelting purification, and the technology is mature, and the purity of Co can reach 5N at most. However, the extractant or the exchange resin used in purifying the cobalt salt solution can introduce new impurities into the electrolytic system, and in the electrolytic refining production process, the conditions of main Co ion concentration, temperature, current density, pH value of the solution and the like must be strictly controlled, and because the impurities such as Cu, ni, fe and the like are difficult to directly remove, additional impurity removing steps are required to be added in the preparation process, the operation is complex, and the overall cost is high.
Use of H by G.Glebovsky et al 2 Reduction of CoCl 2 Using electron beam regions in combinationA method for preparing high-purity cobalt by a fusion method. The process uses H at the temperature of 750-800 DEG C 2 Reduction of high purity CoCl 2 And (3) continuously annealing the obtained Co powder in a chlorine gas flow for 1h, and finally growing Co crystals by using an electron beam zone melting method, wherein impurities are not effectively removed, and the obtained Co crystals can not meet the purity requirements of high-purity Co targets and atomic layer deposition precursors for manufacturing integrated circuit chips.
Disclosure of Invention
Therefore, the method for preparing the high-purity cobalt provided by the invention has the advantages that the cobalt salt is pretreated before undergoing the reduction reaction to remove part of impurities, so that the impurity content in the high-purity cobalt can be effectively reduced, the operation steps are simplified, and the cost is reduced.
Specifically, the invention provides a method for preparing high-purity cobalt, which comprises the steps of mixing cobalt salt with a precipitator, precipitating, filtering, and concentrating the obtained filtrate to obtain the high-purity cobalt salt; then reducing the high-purity cobalt salt to obtain high-purity cobalt; wherein the precipitant is one or more selected from ammonium bisulfide, hydrogen sulfide, ammonia gas and ammonia water.
The invention discovers that the precipitant is added into cobalt salt, so that metal impurity ions such as Cu, fe, cr, ni in the cobalt salt can be converted into corresponding metal sulfide and/or hydroxide precipitates, which is beneficial to reducing the content of the metal impurity ions in the cobalt salt, improving the purity of the cobalt salt and further improving the purity of the metal cobalt.
Preferably, the cobalt salt comprises one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate, and further preferably cobalt chloride.
The precipitant at least contains ammonium bisulfide and ammonia water. The present invention has found that ammonium bisulfide is more efficient in converting trace metal impurity ions in cobalt salts to metal sulfides such as CuS, feS, crS, niS, etc., than hydrogen sulfide; compared with ammonia, the ammonia water using process is safer and more controllable.
Preferably, the dosage of the ammonium bisulfide is 0.001-2% of the mass of the cobalt salt; the dosage of the ammonia water is 0.001-2% of the mass of the cobalt salt. By adopting the dosage ratio, the content of metal impurity ions in the cobalt salt can be sufficiently reduced, meanwhile, the loss caused by the conversion of cobalt ions into cobalt sulfide and/or cobalt hydroxide can be reduced, and the yield of high-purity cobalt salt can be improved.
The ammonium bisulfide used in this discovery is commercially available and can also be prepared by the following method: to contain about 125 g Na 2 S, gradually dripping 36-38% hydrochloric acid into the three-neck flask, and collecting generated gas H 2 S, and will generate H 2 S is filled with 500ml of dilute ammonia water solution (pure water: ammonia water volume ratio is 4:1) for collection, and when Na 2 When S is completely dissolved, stopping dripping hydrochloric acid.
Preferably, the method for concentrating the obtained filtrate specifically comprises the following steps: heating the filtrate until a crystal film appears on the surface, cooling to room temperature through repeated stirring and standing steps, and then filtering; wherein the heating temperature is 160-200 ℃, preferably 175-185 ℃; the stirring speed is 30-120 rpm, and the stirring time is 1.5-2.5 minutes each time; the time of each standing is 0.5-1.5 minutes. The invention further finds that under the crystallization conditions, the purity of cobalt salt is further improved, and the purity of cobalt obtained by the reduction reaction is further improved.
Preferably, the reduction reaction specifically includes: reacting the high-purity cobalt salt with hydrogen at a reduction temperature of 600-900 ℃; the reduction temperature is preferably 800 to 900 ℃.
Further preferably, the high purity cobalt salt is heated to 500+ -50deg.C under inert atmosphere, then mixed with hydrogen, and then heated to reduction temperature.
Preferably, the temperature is raised to the reduction temperature by a step temperature raising method, and the step temperature raising program is as follows:
heating from room temperature to 50+/-5 ℃ through heating for 45-55 min;
heating from 50+/-5 ℃ to 70+/-5 ℃ through heating for 55-65 min;
heating from 70+/-5 ℃ to 100+/-5 ℃ through heating for 25-35 min;
heating from 100+/-5 ℃ to 160+/-10 ℃ through heating for 110-130 min;
heating from 160+/-10 ℃ to 200+/-10 ℃ through heating for 35-45 min;
heating from 200+/-10 ℃ to 600+/-50 ℃ through heating for 35-45 min, and preserving heat at 600+/-50 ℃ for 55-65 min;
and heating from 600+/-50 ℃ to the reduction temperature through heating for 25-35 min, and preserving heat for 55-65 min. The invention further discovers that the reduction effect of cobalt can be greatly improved by carrying out the step heating on the purified cobalt salt, thereby being more beneficial to improving the purity of cobalt.
And/or the mode of mixing the high-purity cobalt salt with hydrogen is specifically as follows: hydrogen was introduced into the apparatus containing the highly pure cobalt salt at a rate of 1.+ -. 0.2L/min.
More preferably, the method for preparing high purity cobalt comprises the following steps:
1) Mixing cobalt salt and a precipitator, precipitating and filtering, heating the obtained filtrate until a crystal film appears on the surface, cooling to room temperature through repeated stirring and standing steps, and filtering to obtain high-purity cobalt salt, wherein the heating temperature is 160-200 ℃; the stirring speed is 30-120 rpm, and the stirring time is 1.5-2.5 minutes each time; the standing time is 0.5-1.5 minutes each time;
2) After the high-purity cobalt salt is heated to 500+/-50 ℃ in an inert atmosphere, hydrogen is introduced at a rate of 1+/-0.2L/min, and then the temperature is continuously raised to 600-900 ℃, wherein the temperature is raised to the reduction temperature in a step heating mode, and the step heating program is as follows:
heating from room temperature to 50+/-5 ℃ through heating for 45-55 min;
heating from 50+/-5 ℃ to 70+/-5 ℃ through heating for 55-65 min;
heating from 70+/-5 ℃ to 100+/-5 ℃ through heating for 25-35 min;
heating from 100+/-5 ℃ to 160+/-10 ℃ through heating for 110-130 min;
heating from 160+/-10 ℃ to 200+/-10 ℃ through heating for 35-45 min;
heating from 200+/-10 ℃ to 600+/-50 ℃ through heating for 35-45 min, and preserving heat at 600+/-50 ℃ for 55-65 min;
and heating from 600+/-50 ℃ to the reduction temperature through heating for 25-35 min, and preserving heat for 55-65 min.
The invention provides the high-purity cobalt prepared by the method.
The invention provides application of the high-purity cobalt in sputtering targets in the preparation process of atomic layer deposition precursors, integrated circuit chips and magnetic recording media.
Based on the technical scheme, the invention has the following beneficial effects:
the method can effectively remove the impurities in the cobalt salt, avoids introducing new impurities in the impurity removal process, has high purity of the prepared cobalt, low content of copper, iron, nickel, chromium and manganese as metal impurities, and excellent product quality, and has strong operability, low cost and wide application prospect.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The embodiment provides a method for preparing high-purity cobalt, which comprises the following steps:
1) 800g of cobalt chloride hexahydrate with the purity of 99.5 percent is dissolved in 1000ml of water, 2 g of ammonium bisulfide is added, stirring is continuously carried out while adding, and stirring is carried out for 2 minutes after the addition is finished. Then adding 12ml ammonia water (the concentration is 25-28%), stirring continuously while adding, standing for 120 min, and filtering;
2) Drying the obtained filtrate in a drying box at 180deg.C until crystal film appears on the surface, taking out, placing in a basin containing water, stirring at 60rpm for 2 min, standing for 1 min, repeating the above stirring and standing steps until the filtrate temperature approaches room temperature, and pouring the solution into a pumpSeparating mother liquor in a filter container to obtain high-purity cobalt salt CoCl 2 ·6H 2 O；
3) High purity CoCl 2 ·6H 2 Placing O in a quartz boat, placing the quartz boat in a quartz tube, vacuumizing to 50Pa by a vacuum pump, and then introducing N at 0.5L/min 2 Heating to 900 deg.C according to the step heating program shown in Table 1, stopping pumping when the temperature in quartz tube reaches 240 deg.C, and introducing N at 1L/min 2 To one atmosphere. When the temperature in the quartz tube reaches 500 ℃, H is introduced at 1L/min 2 。
TABLE 1 temperature increasing program
4) When the temperature in the quartz tube reaches 900 ℃, the quartz tube is kept for 1 hour, and is cooled to room temperature along with the furnace under the protection of hydrogen.
157.4g of high purity cobalt product was obtained, and the yield of cobalt was 80%. Trace impurity analysis was performed on high purity cobalt using Glow Discharge Mass Spectrometry (GDMS) and the results are shown in table 2.
TABLE 2 Glow Discharge Mass Spectrometry (GDMS) analysis results
The purity of the high-purity cobalt of the embodiment is 99.9992% (without four elements of C, H, O and N), wherein the content of metal impurities such as Cu, fe, cr and Mn is greatly reduced, and the high-purity cobalt has excellent product performance.
Comparative example 1
The preparation method provided in this comparative example differs from that of example 1 in that steps 1) and 2) are omitted and cobalt chloride hexahydrate having a purity of 99.5% is directly subjected to hydrogen reduction of step 3).
191g of high purity cobalt product was obtained, and the yield of cobalt was 97%. The results of Glow Discharge Mass Spectrometry (GDMS) detection of the obtained high-purity cobalt are shown in Table 3.
TABLE 3 Glow Discharge Mass Spectrometry (GDMS) analysis results
The purity of the high purity cobalt of this comparative example was 99.986% (without the four elements of C, H, O, N).
Comparative example 2
The preparation method provided in this comparative example differs from that of example 1 in that step 1) was omitted and cobalt chloride hexahydrate having a purity of 99.5% was directly subjected to steps 2) and 3).
167g of high purity cobalt product was obtained, and the yield of cobalt was 85%. The results of Glow Discharge Mass Spectrometry (GDMS) detection of the obtained high-purity cobalt are shown in Table 4.
TABLE 4 Glow Discharge Mass Spectrometry (GDMS) analysis results
The purity of the high purity cobalt of this comparative example was 99.9985% (without the four elements of C, H, O, N).
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A method of producing high purity cobalt comprising:
mixing cobalt salt with a precipitator, precipitating, filtering, heating the obtained filtrate until a crystal film appears on the surface, cooling to room temperature through repeated stirring and standing steps, and filtering to obtain high-purity cobalt salt; then heating the high-purity cobalt salt to 500+/-50 ℃ in an inert atmosphere, mixing with hydrogen, and continuously heating to the reduction temperature of 800-900 ℃; wherein the precipitant is ammonium bisulfide and ammonia water;
the dosage of the ammonium bisulfide is 0.001-2% of the mass of cobalt salt;
the dosage of the ammonia water is 0.001-2% of the mass of cobalt salt;
heating to a reduction temperature in a step heating mode, wherein the step heating program is as follows:
heating from room temperature to 50+/-5 ℃ through heating for 45-55 min;
heating from 50+/-5 ℃ to 70+/-5 ℃ through heating for 55-65 min;
heating from 70+/-5 ℃ to 100+/-5 ℃ through heating for 25-35 min;
heating from 100+/-5 ℃ to 160+/-10 ℃ through heating for 110-130 min;
heating from 160+/-10 ℃ to 200+/-10 ℃ through heating for 35-45 min;
heating from 200+/-10 ℃ to 600+/-50 ℃ through heating for 35-45 min, and preserving heat for 55-65 min at 600+/-50 ℃;
and heating from 600+/-50 ℃ to the reduction temperature through heating for 25-35 min, and preserving heat for 55-65 min.
2. The method of producing high purity cobalt according to claim 1 wherein the cobalt salt comprises one or more of cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt acetate.
3. The method for preparing high-purity cobalt according to claim 1, wherein the heating temperature of the filtrate is 160-200 ℃; the stirring speed is 30-120 rpm, and the stirring time is 1.5-2.5 minutes each time; the time of each standing is 0.5-1.5 minutes.
4. The method for preparing high purity cobalt according to claim 3, wherein the heating temperature of the filtrate is 175-185 ℃.
5. The method for preparing high purity cobalt according to claim 1, wherein the high purity cobalt salt is mixed with hydrogen in the following manner: hydrogen was introduced into the apparatus containing the highly pure cobalt salt at a rate of 1.+ -. 0.2L/min.
6. High purity cobalt, characterized in that it is produced by the process according to any one of claims 1-5.
7. Use of the high purity cobalt according to claim 6 in sputter targets in atomic layer deposition precursors, integrated circuit chips and magnetic recording medium manufacturing processes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111439462.XA CN114192792B (en) | 2021-11-30 | 2021-11-30 | Method for preparing high-purity cobalt and application thereof |
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| JP3122948B1 (en) * | 1999-07-02 | 2001-01-09 | 株式会社高純度化学研究所 | Method for producing high purity cobalt |
| KR20010084867A (en) * | 2000-02-29 | 2001-09-06 | 박청식 | Process for the production of extra fine powder of Cobalt |
| CN1817517A (en) * | 2004-12-06 | 2006-08-16 | 深圳市格林美高新技术有限公司 | Production and producing apparatus for super fine cobalt powder by circulating technology |
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| CN102910687A (en) * | 2012-11-07 | 2013-02-06 | 天津市化学试剂研究所 | Preparation method of superior pure cobalt chloride |
| CN109550972A (en) * | 2019-01-22 | 2019-04-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of high temperature cemented carbide cobalt powder |
| CN113387402A (en) * | 2021-07-08 | 2021-09-14 | 四川顺应动力电池材料有限公司 | Method for producing nickel cobalt sulfate by using nickel cobalt hydroxide raw material crystallization method |
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| US4184868A (en) * | 1978-05-31 | 1980-01-22 | Gte Sylvania Incorporated | Method for producing extra fine cobalt metal powder |
| US4329169A (en) * | 1980-08-18 | 1982-05-11 | Gte Products Corporation | Method for producing cobalt metal powder |
| JP3122948B1 (en) * | 1999-07-02 | 2001-01-09 | 株式会社高純度化学研究所 | Method for producing high purity cobalt |
| KR20010084867A (en) * | 2000-02-29 | 2001-09-06 | 박청식 | Process for the production of extra fine powder of Cobalt |
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| CN102049524A (en) * | 2009-10-29 | 2011-05-11 | 北京有色金属研究总院 | Method for preparing nano Epsilon-Co powder |
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| CN109550972A (en) * | 2019-01-22 | 2019-04-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of high temperature cemented carbide cobalt powder |
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