CN110961650A - Preparation method of zirconium-doped superfine nickel powder - Google Patents
Preparation method of zirconium-doped superfine nickel powder Download PDFInfo
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- CN110961650A CN110961650A CN201811139468.3A CN201811139468A CN110961650A CN 110961650 A CN110961650 A CN 110961650A CN 201811139468 A CN201811139468 A CN 201811139468A CN 110961650 A CN110961650 A CN 110961650A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 101
- 239000000843 powder Substances 0.000 claims abstract description 99
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000012716 precipitator Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- 239000001099 ammonium carbonate Substances 0.000 claims description 36
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 15
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 235000017550 sodium carbonate Nutrition 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 15
- 229910045601 alloy Inorganic materials 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 6
- ZSJFLDUTBDIFLJ-UHFFFAOYSA-N nickel zirconium Chemical compound [Ni].[Zr] ZSJFLDUTBDIFLJ-UHFFFAOYSA-N 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 12
- 238000005054 agglomeration Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910003126 Zr–Ni Inorganic materials 0.000 description 8
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
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- B22F1/0003—
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- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a preparation method of zirconium-doped superfine nickel powder, which comprises the steps of mixing a first precipitator and ZrO2Adding powder into a reaction kettle, heating the reaction kettle, adding nickel salt, a second precipitator and a surfactant into the reaction kettle, controlling the feeding flow of the nickel salt and the second precipitator to keep the pH value of a reaction system at 7.2-9.2, and obtaining the wrapped ZrO2Then wrapping ZrO with the basic nickel salt precursor2Carrying out high-temperature hydrogen reduction on the basic nickel salt powder to obtain zirconium-doped superfine nickel powder; thus, the invention is doped in the process of preparing the basic nickel salt precursor and then wraps ZrO2The basic nickel salt precursor is calcined at high temperature to obtain the wrapped ZrO2The basic nickel salt powder can effectively avoid the phenomenon of uneven mixing of zirconium-nickel composite powder, the obtained zirconium-doped superfine nickel powder has good uniformity, and the red hardness of the nickel powder in alloy application can be enhancedRed heat toughness.
Description
Technical Field
The invention belongs to the technical field of nickel powder preparation, and particularly relates to a preparation method of zirconium-doped superfine nickel powder.
Background
The superfine nickel powder is a good electric and magnetic heat sensitive material, and has wide application prospect in the aspects of catalysts, magnetic materials, sintering activators, conductive slurry, battery materials, hard alloy binders and the like.
At present, many alloys are mixed with zirconium powder for use, and the traditional manufacturing method of zirconium-nickel composite powder comprises a mechanical mixing method and an atomization method, and the zirconium-nickel composite powder manufactured by the two methods is not uniformly mixed, so that the alloy has more defects easily, and the service life of the alloy is influenced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of zirconium-doped superfine nickel powder.
The invention provides a preparation method of zirconium-doped superfine nickel powder, which is implemented by the following steps:
step 1, adding a first precipitator into a reaction kettle to serve as a base solution, stirring the base solution at a stirring frequency of 25Hz, and adding ZrO into the first precipitator2Powder is stirred for 30-60 min until the ZrO is obtained2Dispersing powder into a first precipitator, heating the reaction kettle to 60-70 ℃ and keeping the temperature constant, adding nickel salt, a second precipitator and a surfactant into the reaction kettle, controlling the feeding flow of the nickel salt and the second precipitator to keep the pH value of a reaction system at 7.2-9.2, and reacting for 3-5 hours to obtain the coated ZrO2The basic nickel salt precursor;
step 2, adopting pure water to pack ZrO obtained in the step 12Basic nickel salt precursor ofWashing, drying after washing to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping the ZrO obtained in the step 22The basic nickel salt powder is crushed by airflow and then is reduced by high-temperature hydrogen to obtain the zirconium-doped superfine nickel powder.
In the above scheme, ZrO added in the step 12The mass ratio of the powder to the nickel salt is 1: 200-2: 200.
In the above scheme, the nickel salt in step 1 is one of a nickel nitrate solution, a nickel sulfate solution or a nickel chloride solution.
In the scheme, the nickel content of the nickel salt in the step 1 is 2mol/L, and the feeding flow rate of the nickel salt is 200L/H.
In the above scheme, in step 1, the first precipitant and the second precipitant are both one of sodium carbonate, ammonium bicarbonate, ammonium carbonate or sodium hydroxide.
In the scheme, the volume of the first precipitator added in the step 1 is 400-500L, and the concentration of the first precipitator is 0.05 mol/L.
In the scheme, the volume ratio of the second precipitator to the nickel salt added in the step 1 is 1.8: 1-2.5: 1, the concentration of the second precipitator is 2mol/L, and the feeding flow rate of the second precipitator is 400L/H.
In the above scheme, the surfactant in step 1 is one of (L) -tartaric acid, citric acid or oxalic acid.
In the scheme, the volume of the surfactant added in the step 1 is 8-16L.
In the scheme, the reduction temperature of the high-temperature hydrogen reduction in the step 3 is 600-700 ℃, and the reduction time is 2-3 h.
Compared with the prior art, the invention carries out doping in the process of preparing the basic nickel salt precursor to obtain the wrapped ZrO2The basic nickel salt precursor is then coated with ZrO2The basic nickel salt precursor is calcined at high temperature to obtain the wrapped ZrO2The basic nickel salt powder can effectively avoid the phenomenon of uneven mixing of the zirconium-nickel composite powderThe obtained zirconium-doped superfine nickel powder has good uniformity, and can enhance the red hardness and the red heat toughness of the nickel powder in alloy application.
Drawings
Fig. 1 is a scanning electron microscope image of a method for preparing zirconium-doped ultrafine nickel powder according to embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of zirconium-doped superfine nickel powder, which is implemented by the following steps:
step 1, adding 400L-500L of first precipitator with the concentration of 0.05mol/L into a reaction kettle to be used as base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the first precipitator2Powder, added ZrO2The mass ratio of the powder to the nickel salt is 1: 200-2: 200, and the mixture is stirred for 30-60 min to ZrO2Dispersing the powder in a first precipitator, heating a reaction kettle to 60-70 ℃ and keeping the temperature constant, adding nickel salt with the nickel content of 2mol/L into the reaction kettle at the feeding flow of 200L/H by using a metering pump, adding a second precipitator with the concentration of 2mol/L into the reaction kettle at the feeding flow of 400L/H, wherein the volume ratio of the second precipitator to the nickel salt is 1.8: 1-2.5: 1, simultaneously adding 8-16L of surfactant to keep the pH value of a reaction system at 7.2-9.2, and reacting for 3-5H to obtain the coated ZrO2The basic nickel salt precursor;
wherein the nickel salt is one of nickel nitrate solution, nickel sulfate solution or nickel chloride solution; the first precipitator and the second precipitator are both one of sodium carbonate, ammonium bicarbonate, ammonium carbonate or sodium hydroxide; the surfactant is one of (L) -tartaric acid, citric acid or oxalic acid;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine,washing with pure water at the temperature of 60-80 ℃ for 4-6 times, placing the washed mixture in a flash evaporation machine, and drying at the temperature of 60-80 ℃ to obtain the coated ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 2 to 3 hours by high-temperature hydrogen at the reduction temperature of 600 to 700 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
The invention is doped in the process of preparing the basic nickel salt precursor to obtain the wrapped ZrO2The basic nickel salt precursor is then coated with ZrO2The basic nickel salt precursor is calcined at high temperature to obtain the wrapped ZrO2The basic nickel salt powder can effectively avoid the phenomenon of uneven mixing of zirconium-nickel composite powder, the obtained zirconium-doped superfine nickel powder has good uniformity, the bonding property of the nickel powder in alloy application can be enhanced, and the red hardness and red heat toughness of the composite material are improved. The method of twice precipitating agents can effectively control the particle size distribution of the precursor of the prepared nickel powder, thereby controlling the particle size distribution of the nickel powder; the obtained product can be directly used for alloy mixing by controlling the mass ratio of zirconium to nickel, so that the application range of the zirconium-nickel powder is enlarged; ZrO is greatly enhanced by the addition of small amounts of surfactants2And the nickel powder precursor, thereby avoiding a large amount of agglomeration, enhancing the applicability of the zirconium-doped nickel powder in the alloy tool industry, and effectively weakening the limitation of the alloy tool performance caused by uneven mixing in the alloy production process.
Example 1
Embodiment 1 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 400L of sodium carbonate with the concentration of 0.05mol/L into a reaction kettle to be used as base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the sodium carbonate2Powder, added ZrO2The mass ratio of the powder to the nickel nitrate solution is 1:200, and the mixture is stirred for 30min to ZrO2Dispersing the powder in sodium carbonate, heating the reaction kettle to 60 deg.C, keeping constant temperature, and metering with a metering pump at a rate of 200L/HAdding a nickel nitrate solution with the nickel content of 2mol/L into a reaction kettle at the feeding flow rate of 400L/H, adding sodium carbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow rate of 400L/H, wherein the volume ratio of the sodium carbonate to the nickel nitrate solution is 2:1, simultaneously adding 12L of (L) -tartaric acid to keep the pH value of a reaction system at 7.2-9.2, and reacting for 4H to obtain the ZrO coated ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 72 ℃, put into a flash evaporation machine after washing, and dried at 70 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 2.8 hours by high-temperature hydrogen at the reduction temperature of 660 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
As shown in fig. 1, it can be seen from a scanning electron microscope image of the method for preparing zirconium-doped ultrafine nickel powder provided in embodiment 1 that the Zr — Ni powder is uniformly mixed and distributed without individual agglomeration.
Example 2
Embodiment 2 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 450L of sodium carbonate with the concentration of 0.05mol/L into a reaction kettle to be used as base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the sodium carbonate2Powder, added ZrO2The mass ratio of the powder to the nickel nitrate solution is 1.5:200, and the mixture is stirred for 45min until ZrO is achieved2Dispersing the powder in sodium carbonate, heating a reaction kettle to 66 ℃ and keeping the temperature constant, adding a nickel nitrate solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow of 200L/H by using a metering pump, adding sodium carbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow of 400L/H, wherein the volume ratio of the sodium carbonate to the nickel nitrate solution is 2:1, simultaneously adding 12L of (L) -tartaric acid to keep the pH value of a reaction system at 7.2-9.2, and reacting for 4 hours to obtain the ZrO coated ZrO2Basic nickel salt precursor of；
Step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 72 ℃, put into a flash evaporation machine after washing, and dried at 70 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 2.8 hours by high-temperature hydrogen at the reduction temperature of 660 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 3
Embodiment 3 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 500L of sodium carbonate with the concentration of 0.05mol/L into a reaction kettle to be used as base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the sodium carbonate2Powder, added ZrO2The mass ratio of the powder to the nickel nitrate solution is 2:200, and the mixture is stirred for 60min to ZrO2Dispersing the powder in sodium carbonate, heating a reaction kettle to 70 ℃ and keeping the temperature constant, adding a nickel nitrate solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow rate of 200L/H by using a metering pump, adding sodium carbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow rate of 400L/H, wherein the volume ratio of the sodium carbonate to the nickel nitrate solution is 2:1, simultaneously adding 12L of (L) -tartaric acid to keep the pH value of a reaction system at 7.2-9.2, and reacting for 4 hours to obtain the ZrO coated ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 72 ℃, put into a flash evaporation machine after washing, and dried at 70 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22Basic group ofAnd crushing the nickel salt powder by airflow, then putting the crushed nickel salt powder into a reduction furnace, reducing the crushed nickel salt powder for 2.8 hours by high-temperature hydrogen at the reduction temperature of 660 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 4
Embodiment 4 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 500L of ammonium bicarbonate with the concentration of 0.05mol/L into a reaction kettle to be used as a base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the ammonium bicarbonate2Powder, added ZrO2The mass ratio of the powder to the nickel sulfate solution is 1:200, and the mixture is stirred for 40min to ZrO2Dispersing the powder in ammonium bicarbonate, heating a reaction kettle to 68 ℃ and keeping the temperature constant, adding a nickel sulfate solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow of 200L/H by using a metering pump, adding ammonium bicarbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow of 400L/H, wherein the volume ratio of the ammonium bicarbonate to the nickel sulfate solution is 1.8:1, simultaneously adding 8L of citric acid to keep the pH value of a reaction system at 7.2-9.2, and reacting for 3 hours to obtain the ZrO coated ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 70 ℃, then put into a flash evaporation machine after washing, and dried at 60 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 3 hours by high-temperature hydrogen at the reduction temperature of 640 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 5
Embodiment 5 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 500L of ammonium bicarbonate with the concentration of 0.05mol/L into a reaction kettle to be used as a base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the ammonium bicarbonate2Powder, added ZrO2The mass ratio of the powder to the nickel sulfate solution is 1:200, and the mixture is stirred for 40min to ZrO2Dispersing the powder in ammonium bicarbonate, heating a reaction kettle to 68 ℃ and keeping the temperature constant, adding a nickel sulfate solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow rate of 200L/H by using a metering pump, adding ammonium bicarbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow rate of 400L/H, wherein the volume ratio of the ammonium bicarbonate to the nickel sulfate solution is 2.3:1, simultaneously adding 12L of citric acid to keep the pH value of a reaction system at 7.2-9.2, and reacting for 4 hours to obtain the ZrO coated ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 70 ℃, then put into a flash evaporation machine after washing, and dried at 60 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 3 hours by high-temperature hydrogen at the reduction temperature of 640 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 6
Embodiment 6 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 500L of ammonium bicarbonate with the concentration of 0.05mol/L into a reaction kettle to be used as a base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the ammonium bicarbonate2Powder of, addingZrO of2The mass ratio of the powder to the nickel sulfate solution is 1:200, and the mixture is stirred for 40min to ZrO2Dispersing the powder in ammonium bicarbonate, heating a reaction kettle to 68 ℃ and keeping the temperature constant, adding a nickel sulfate solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow rate of 200L/H by using a metering pump, adding ammonium bicarbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow rate of 400L/H, wherein the volume ratio of the ammonium bicarbonate to the nickel sulfate solution is 2.5:1, simultaneously adding 16L of citric acid to keep the pH value of a reaction system at 7.2-9.2, and reacting for 5 hours to obtain the ZrO coated ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 70 ℃, then put into a flash evaporation machine after washing, and dried at 60 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 3 hours by high-temperature hydrogen at the reduction temperature of 640 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 7
Embodiment 7 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 400L of ammonium carbonate with the concentration of 0.05mol/L into a reaction kettle to be used as a base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the ammonium carbonate2Powder, added ZrO2The mass ratio of the powder to the nickel chloride solution is 2:200, and the mixture is stirred for 60min to ZrO2Dispersing the powder in ammonium carbonate, heating the reaction kettle to 65 ℃ and keeping the temperature constant, adding a nickel chloride solution with the nickel content of 2mol/L into the reaction kettle at a feeding flow of 200L/H by using a metering pump, and adding ammonium carbonate and ammonium carbonate with the concentration of 2mol/L into the reaction kettle at a feeding flow of 400L/HThe volume ratio of the solution to the nickel chloride solution is 2:1, 12L of oxalic acid is added at the same time, the pH value of the reaction system is kept between 7.2 and 9.2, the reaction is carried out for 3.6 hours, and the ZrO coated by the mixture is obtained2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 6 times by pure water at 60 ℃, then put into a flash evaporation machine after washing, and dried at 60 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 3 hours by high-temperature hydrogen at the reduction temperature of 600 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 8
Embodiment 8 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 400L of ammonium carbonate with the concentration of 0.05mol/L into a reaction kettle to be used as a base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the ammonium carbonate2Powder, added ZrO2The mass ratio of the powder to the nickel chloride solution is 2:200, and the mixture is stirred for 60min to ZrO2Dispersing the powder in ammonium carbonate, heating a reaction kettle to 65 ℃ and keeping the temperature constant, adding a nickel chloride solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow rate of 200L/H by using a metering pump, adding ammonium carbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow rate of 400L/H, wherein the volume ratio of the ammonium carbonate to the nickel chloride solution is 2:1, simultaneously adding 12L of oxalic acid to keep the pH value of the reaction system at 7.2-9.2, and reacting for 3.6 hours to obtain the wrapped ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 5 times by pure water at 72 ℃, and then put into a flash evaporation machine after washingDrying at 72 deg.C to obtain coated ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 2.2 hours by high-temperature hydrogen at the reduction temperature of 640 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
Example 9
Embodiment 9 of the present invention provides a method for preparing zirconium-doped ultrafine nickel powder, which is implemented by the following steps:
step 1, adding 400L of ammonium carbonate with the concentration of 0.05mol/L into a reaction kettle to be used as a base solution, stirring the base solution at the stirring frequency of 25Hz, and adding ZrO into the ammonium carbonate2Powder, added ZrO2The mass ratio of the powder to the nickel chloride solution is 2:200, and the mixture is stirred for 60min to ZrO2Dispersing the powder in ammonium carbonate, heating a reaction kettle to 65 ℃ and keeping the temperature constant, adding a nickel chloride solution with the nickel content of 2mol/L into the reaction kettle at the feeding flow rate of 200L/H by using a metering pump, adding ammonium carbonate with the concentration of 2mol/L into the reaction kettle at the feeding flow rate of 400L/H, wherein the volume ratio of the ammonium carbonate to the nickel chloride solution is 2:1, simultaneously adding 12L of oxalic acid to keep the pH value of the reaction system at 7.2-9.2, and reacting for 3.6 hours to obtain the wrapped ZrO2The basic nickel salt precursor;
step 2, wrapping ZrO obtained in the step 12The basic nickel salt precursor is put into a two-in-one washing machine, washed for 4 times by pure water at the temperature of 80 ℃, put into a flash evaporation machine after washing, and dried at the temperature of 80 ℃ to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping ZrO obtained in the step 22And crushing the basic nickel salt powder by airflow, then putting the crushed basic nickel salt powder into a reduction furnace, reducing the crushed basic nickel salt powder for 2 hours by high-temperature hydrogen at the reduction temperature of 700 ℃, and finally removing iron to obtain the zirconium-doped superfine nickel powder.
Compared with the prior art, the zirconium-doped superfine nickel powder obtained by the preparation process has uniform Zr-Ni powder mixing distribution and no independent agglomeration.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (10)
1. The preparation method of the zirconium-doped superfine nickel powder is characterized by comprising the following steps:
step 1, adding a first precipitator into a reaction kettle to serve as a base solution, stirring the base solution at a stirring frequency of 25Hz, and adding ZrO into the first precipitator2Powder is stirred for 30-60 min until the ZrO is obtained2Dispersing powder into a first precipitator, heating the reaction kettle to 60-70 ℃ and keeping the temperature constant, adding nickel salt, a second precipitator and a surfactant into the reaction kettle, controlling the feeding flow of the nickel salt and the second precipitator to keep the pH value of a reaction system at 7.2-9.2, and reacting for 3-5 hours to obtain the coated ZrO2The basic nickel salt precursor;
step 2, adopting pure water to pack ZrO obtained in the step 12The basic nickel salt precursor is washed and then dried to obtain the wrapped ZrO2The basic nickel salt powder of (4);
step 3, wrapping the ZrO obtained in the step 22The basic nickel salt powder is crushed by airflow and then is reduced by high-temperature hydrogen to obtain the zirconium-doped superfine nickel powder.
2. The method of claim 1, wherein ZrO added in step 1 is added2The mass ratio of the powder to the nickel salt is 1: 200-2: 200.
3. The method of claim 2, wherein the nickel salt in step 1 is one of a nickel nitrate solution, a nickel sulfate solution, or a nickel chloride solution.
4. The method of claim 3, wherein the nickel content of the nickel salt in step 1 is 2mol/L, and the feeding flow rate of the nickel salt is 200L/H.
5. The method of claim 4, wherein the first precipitant and the second precipitant are selected from sodium carbonate, ammonium bicarbonate, ammonium carbonate and sodium hydroxide in step 1.
6. The method of claim 5, wherein the volume of the first precipitant added in step 1 is 400-500L, and the concentration of the first precipitant is 0.05 mol/L.
7. The method according to claim 6, wherein the volume ratio of the second precipitant added in step 1 to the nickel salt is 1.8: 1-2.5: 1, the concentration of the second precipitant is 2mol/L, and the feeding flow rate of the second precipitant is 400L/H.
8. The method of claim 7, wherein the surfactant in step 1 is one of (L) -tartaric acid, citric acid, or oxalic acid.
9. The method of claim 8, wherein the volume of the surfactant added in step 1 is 8-16L.
10. The method for preparing zirconium-doped ultrafine nickel powder according to any one of claims 1 to 9, wherein the reduction temperature of the high-temperature hydrogen reduction in step 3 is 600 to 700 ℃ and the reduction time is 2 to 3 hours.
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| CN105921762A (en) * | 2016-06-17 | 2016-09-07 | 陕西理工学院 | Densification formation type preparation method of nickel-based alloy powder |
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| CN1830606A (en) * | 2006-04-14 | 2006-09-13 | 北京科技大学 | Method of preparing ultrafine alloy powder by coprecipitation coreduction |
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