WO2006069513A1 - Spherical ultrafine nickel powder with high tap density and its wet processes preparing mothod - Google Patents

Spherical ultrafine nickel powder with high tap density and its wet processes preparing mothod Download PDF

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Publication number
WO2006069513A1
WO2006069513A1 PCT/CN2005/001861 CN2005001861W WO2006069513A1 WO 2006069513 A1 WO2006069513 A1 WO 2006069513A1 CN 2005001861 W CN2005001861 W CN 2005001861W WO 2006069513 A1 WO2006069513 A1 WO 2006069513A1
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nickel powder
nickel
wet
density
powder according
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PCT/CN2005/001861
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French (fr)
Chinese (zh)
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Guoduan He
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Chengdu Chemphys Chemical Industry Co., Ltd.
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Priority to JP2007548671A priority Critical patent/JP4837675B2/en
Publication of WO2006069513A1 publication Critical patent/WO2006069513A1/en

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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
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the invention belongs to the technical field of manufacturing powder materials, and in particular to a wet manufacturing method of high-vibration density ultra-fine spherical metal nickel powder and a high-vibration ultra-spherical spherical metal nickel powder prepared by the method. Background technique
  • the nickel powder produced by these methods has one or more of the following problems: irregular shape, too small density, too high manufacturing cost, and a wide range of particle size distribution.
  • the method of preparing nickel powder by the solution reduction method is generally carried out in two steps.
  • the first step is to prepare a nickel hydroxide colloid, a nickel carbonate colloid or a nickel basic salt at room temperature, which is a liquid phase nucleation reaction;
  • the second step is to reduce the nickel hydroxide colloid, the nickel carbonate colloid or the hydrated hydrazine under a certain temperature condition.
  • the basic salt of nickel, which forms metal nickel powder belongs to the oxidation-reduction reaction.
  • the basic chemical reaction of the two steps is -
  • JP4-74810 discloses a nickel powder prepared by reducing a nickel salt by using a hydrazine hydrate and a hypophosphorous acid (or sodium borohydride) mixed reducing agent, which has a small density, a large particle size, an irregular shape, and agglomeration.
  • Japanese Patent No. Hei 5-51610 discloses a method for directly reducing Ni(OH) 2 using a ruthenium or osmium compound.
  • the nickel powder obtained by the method has a small density, a large particle size, a wide powder distribution, and poor process stability.
  • JP 8-246001 discloses a nickel powder prepared by a vapor phase reduction method using NiCl 2 , which is a high-shear density nickel powder, but has a wide particle size distribution range, high production cost, and great equipment investment, and is not easy to carry out on a large scale. produce.
  • the method consumes a large amount of heating energy, and the NiCl 2 is heated to a vaporization temperature of >900 Q C in the crucible, and the vaporized NiCl 2 vapor is loaded into a specific reaction vessel through Ar (argon) gas, and H 2 gas is introduced at the same time.
  • Nickel powder is produced at a given temperature.
  • the resulting nickel powder is sent to the cooling vessel for indirect cooling under the protection of Ar gas.
  • the heating vaporization, H 2 reaction vessel and cooler of the method are all special equipments, and a large amount of energy consumption and inert gas of Ar gas are used, and the productivity is small and the cost is high. Summary of the invention
  • the object of the present invention is to overcome the above deficiencies and to provide a solution reduction method which can greatly reduce the production cost, the density can be compared with the NiCl 2 vapor phase reduction method, and the particle size distribution range is narrow, which can be easily mass-produced.
  • the invention provides a wet manufacturing method of high-vibration density ultra-micro spherical metal nickel powder, the method comprising the following steps:
  • the above polyol is at least one of glycerol, butyltriol, tetrabutylol and diethylene glycol, and other polyols may also be used.
  • the barium salt is at least one of barium sulfate, barium nitrate, barium chloride, barium acetate, and barium formate, and other barium salts may also be used.
  • the above polyol is added in an amount of 10 to 500% by weight based on the weight of nickel in the reaction system.
  • the above nickel sulfate solution has a molar concentration of 0.1 to 2.5 mol/L.
  • the above-mentioned barium salt is used in an amount of 0.0002 to 0.2% by weight based on the weight of nickel in the reaction system.
  • the above hydrazine or hydrazine has a hydrate concentration of 10 to 80% by weight.
  • the number of moles of the above nickel sulfate [(moles of sodium hydroxide) / 2 moles of sodium carbonate] is 0.39 to 0.94:1.
  • the molar ratio of the hydrazine or hydrazine hydrate to nickel sulfate is from 1.0 to 2.0:1.
  • the present invention also provides a high tap density ultrafine spherical metallic nickel powder produced by the method described above.
  • the above high-density ultrafine spherical metallic nickel powder has an average particle diameter of 0.2 to 1.0 ⁇ m, a particle size distribution of ⁇ 60% of its average particle diameter, and a tap density of more than 3.9 g/cm 3 .
  • Figure 1 is an electron micrograph of a high tap density ultrafine spherical metallic nickel powder prepared in Example 4.
  • Fig. 2 is a graph showing the particle size distribution of the high-shear density ultrafine spherical metallic nickel powder prepared in Example 4.
  • Fig. 3 is an electron micrograph of the high tap density ultrafine spherical metallic nickel powder prepared in Example 3.
  • Fig. 4 is a graph showing the particle size distribution of the high-shear density ultrafine spherical metallic nickel powder prepared in Example 3. detailed description
  • the method of the invention is to react a nickel sulfate solution with a mixed solution of NaOH and Na 2 CO 3 to form a precipitate of M(OH) 2 and NiC0 3 'Ni(OH) 2 , and add a polyol and a phosphonium salt at a pH of 8.5 to 12.5.
  • a hydrate of ruthenium or osmium is added to reduce Ni(OH) 2 and NiC0 3 _Ni(OH) 2 to obtain a high tap density with an average particle diameter of 0.2 ⁇ . ⁇ .
  • Ultra micro spherical metal nickel powder Ultra micro spherical metal nickel powder.
  • the present invention is characterized in that a polyhydric alcohol is added to the reduction system, and its good dispersion and unique adsorption properties are utilized to effectively prevent agglomeration of nickel powder during reduction.
  • a polyhydric alcohol is added to the reduction system, and its good dispersion and unique adsorption properties are utilized to effectively prevent agglomeration of nickel powder during reduction.
  • the growth of the nickel powder particles in all directions tends to be uniform, so that the produced nickel powder has good hooking property, smooth surface and good sphericity.
  • the addition of the cerium salt nucleating agent ensures that the oxidation-reduction reaction proceeds smoothly and stably, and at the same time, the nickel and magnetic properties are weakened, so that the formation of nickel powder during the reduction is more dense, thereby obtaining a high-density nickel powder.
  • the invention can prepare a high-vibration density with an average particle diameter of 0.2 ⁇ 1 ⁇ and a controllable particle size, and a spherical metal nickel powder having a large tap density, a smooth surface and a low oxidation rate (oxygen content ⁇ 0.5%). Strong oxidation resistance (120 ⁇ 140°C does not increase oxygen content when placed in air for 2 hours), the particle size distribution range is narrow, as shown in the following table - Average particle size distribution, tap density, specific surface area
  • the invention can greatly reduce environmental pollution, has low equipment investment, low production cost, and is suitable for large industrial production.
  • the produced nickel powder can be widely used in multilayer ceramic chip capacitors (MLCC) and powders.
  • MLCC multilayer ceramic chip capacitors
  • the solution used in the present invention is distilled water, acid, and alkali, and the raw material is a relatively pure industrial product. In the production process, there is no COD organic oxygen consumption discharge; the mother liquor can be recycled; the overflow of trace ammonia-containing tail gas is pumped into the acid tank and reacted with sulfuric acid to form ammonium sulfate; no dust or waste residue is generated, and the process operation has little environmental pollution.
  • JSM-5900 electronic scanning microscope, manufactured by NEC Corporation, Japan was obtained by SEM test under the following conditions: 20 KU, 10000 to 20000 magnification.
  • the detection data is obtained by DIP method (Digital image processing), and the microscopic digital image analysis system is the supporting software of JSM-5900 electron microscope.
  • the data was obtained by a JZ-1 tap density meter (manufactured by China CDGX Corporation).
  • Oxygen content The data was obtained by TC-434 Nitrogen Analyzer (manufactured by LECO, USA). The test conditions were: sample lg, The He carrier gas was introduced, the temperature was measured at 3000 ° C, and the measurement time was 40 seconds.
  • the test conditions are: 0.6g of sample is degassed and pretreated for 2 hours under vacuum condition of 150 Q C, and the adsorption medium is high. Pure nitrogen, measured at 77.35K liquid nitrogen temperature.
  • Example 1
  • the nickel powder prepared by the above method was observed to have a regular spherical shape under a 20,000-fold electron microscope, and the surface was smooth, the average particle diameter was 0.9 ⁇ m, the particle size distribution range was 0.5 to 1.2 ⁇ m, and the tap density was 4.85 g/cm 3 .
  • the content is 0.28%, and the specific surface area is 1.13 m 2 /g.
  • the nickel powder obtained by the above method was observed to have a regular spherical shape under a 20,000-fold electron microscope, the surface was smooth, the average particle diameter was 0.8 ⁇ m, the particle size distribution range was 0.5 to 1.2 ⁇ , the tap density was 4.7 g/cm 3 , and the oxygen content was obtained. 0.37%, specific surface area is 1.21 m 2 /g.
  • Example 3
  • Example 4 (See Figures 3 and 4), the sphericity is good, the surface is smooth, the particle size distribution is narrow, the tap density is 4.65 g/cm 3 , the oxygen content is 0.38%, and the specific surface area is 1.28 m 2 /g.
  • Example 4 .
  • the nickel powder prepared by the above method is spherical under the electron microscope of 20,000 times, has a surface-like shape, an average particle diameter of 0.9 ⁇ m, a particle size distribution range of 0.3 to 2.5 ⁇ , and a tap density of 2.5 g/cm 3 .
  • the oxygen content was 1.28% and the specific surface area was 8.26 m 2 /g. Comparative example
  • the nickel powder prepared by the above method is observed to have a regular spherical shape under a 20,000-fold electron microscope, and has a smooth surface, an average particle diameter of ⁇ . ⁇ , a particle size distribution range of 0.5 to 1.3 ⁇ , a tap density of 4.5 g/cm 3 , and oxygen. The content is 0.38% and the specific surface area is 1.25 m 2 /g. Comparative Example 3:
  • the nickel powder prepared by the above method is spherical under the electron microscope of 20,000 times, the surface is not smooth, the average particle diameter is 0.82 ⁇ , the particle size distribution range is 0.4 to 1.8 ⁇ , the tap density is 2.8 g/cm 3 , oxygen The content was 1.32% and the specific surface area was 5.63 m 2 /g. Comparative Example 4:

Abstract

The present invention provides a wet processes preparing method of spherical ultrafine nickel powder with high tap density. The method is comprised of using nickel sulfate to react with mixed solution of sodium hydroxide and sodium carbonate to generate nickel hydroxide and basic nickel salt, adding polyhydric alcohol as appearance controlling agent, adding yttrium salt as crystal nucleus forming agent, and using hydrazine or hydrazine hydrate as reducer in order to producing excellent spherical nickel powder with high tap density, narrow grain size distributing, strong resist­oxidation, good dispersivity, and mean grain size 0.2-lµm.The invention increases the tap density of nickel powder prapared by wet processes and decreases environment pollution and production cost greatly. Nickel powder prepared by the invention is used to microelectronics laminated ceramic capacitor, powder metallurgy, magnetic material and so on.

Description

高振实密度超微球形金属镍粉及其湿法制造方法 技术领域  High-vibration density ultra-fine spherical metal nickel powder and wet manufacturing method thereof
本发明属于粉体材料的制造技术领域， 具体而言， 本发明涉及一种高振实密度超 微球形金属镍粉的湿法制造方法及由该方法制备的高振实密度超微球形金属镍粉。 背景技术  The invention belongs to the technical field of manufacturing powder materials, and in particular to a wet manufacturing method of high-vibration density ultra-fine spherical metal nickel powder and a high-vibration ultra-spherical spherical metal nickel powder prepared by the method. Background technique
已有的制备金属镍粉的方法很多。如： 电解法、羰基热分解法、真空蒸馏冷凝法、 机械粉碎法、 浆化髙压氢还原法和溶液还原法等。 这些方法制得的镍粉存在以下问题 中的一种或多种： 形状不规则， 密度太小， 制造成本太高， 和粒径分布范围宽。  There are many methods for preparing metallic nickel powder. Such as: electrolysis, carbonyl thermal decomposition, vacuum distillation condensation, mechanical pulverization, slurry hydrostatic reduction and solution reduction. The nickel powder produced by these methods has one or more of the following problems: irregular shape, too small density, too high manufacturing cost, and a wide range of particle size distribution.
在这些方法中， 对溶液还原法进行了很多研究。 由溶液还原法制备镍粉的方法一 般都是通过两步完成。 第一步在常温下制备出氢氧化镍胶体、 碳酸镍胶体或镍的碱式 盐， 属液相成核反应； 第二步在一定温度条件下用水合肼还原氢氧化镍胶体、 碳酸镍 胶体或镍的碱式盐， 生成金属镍粉， 属氧化一还原反应， 两步的基本化学反应为-  Among these methods, many studies have been conducted on the solution reduction method. The method of preparing nickel powder by the solution reduction method is generally carried out in two steps. The first step is to prepare a nickel hydroxide colloid, a nickel carbonate colloid or a nickel basic salt at room temperature, which is a liquid phase nucleation reaction; the second step is to reduce the nickel hydroxide colloid, the nickel carbonate colloid or the hydrated hydrazine under a certain temperature condition. The basic salt of nickel, which forms metal nickel powder, belongs to the oxidation-reduction reaction. The basic chemical reaction of the two steps is -
Ni2+ + 20H- ~· > Ni(OH)2 i Ni 2+ + 20H- ~· > Ni(OH) 2 i
2Ni2+ + C03 2- + 20H- ~~ NiC03-Ni(OH)2| 2Ni 2+ + C0 3 2 - + 20H- ~~ NiC0 3 -Ni(OH) 2 |
Ni2+ + C03 2_ ~~ > NiC03 Ni 2+ + C0 3 2_ ~~ > NiC0 3
2Ni(OH)2 + N2H4 ·~ 2Ni +4¾0 + N2个 2Ni(OH) 2 + N 2 H 4 ·~ 2Ni +43⁄40 + N 2
2NiC03'Ni(OH)2 + 2N2¾ ~~ > 4Ni + 3H20 + 2H2C03 + 2N2 t 2NiC0 3 'Ni(OH) 2 + 2N 2 3⁄4 ~~ > 4Ni + 3H 2 0 + 2H 2 C0 3 + 2N 2 t
JP4-74810公开了一种采用水合肼和次亚磷酸 (或硼氢化钠)混合还原剂还原镍盐制 备的镍粉， 其密度小， 粒径偏大， 形状不规则， 团聚严重。 JP4-74810 discloses a nickel powder prepared by reducing a nickel salt by using a hydrazine hydrate and a hypophosphorous acid (or sodium borohydride) mixed reducing agent, which has a small density, a large particle size, an irregular shape, and agglomeration.
日本平 5-51610公开了一种采用肼或肼的化合物直接还原 Ni(OH)2的方法， 由该 方法得到的镍粉密度小， 粒径大， 粉度分布宽， 工艺稳定性差。 Japanese Patent No. Hei 5-51610 discloses a method for directly reducing Ni(OH) 2 using a ruthenium or osmium compound. The nickel powder obtained by the method has a small density, a large particle size, a wide powder distribution, and poor process stability.
上海华东理工大学公开了一种以水合肼为还原剂， 硝酸银为成核剂， PVP为保护 剂制备镍粉的方法。 将 MS04溶液直接滴加到含有 Na2C03、 水合肼及 PVP (聚乙烯吡 咯垸酮)混合液中， 再加入 AgN03成核， 该方法制得的镍粉粒径偏大， PVP用量很大， 成本很高， 且还原过程中有片状镍生成 (参见， "溶液还原法制备球形超细镍粉"， 沈勇 等， 物理化学学报， 1996年 5月， 第 12卷第 5期； 和 "高分子保护溶液还原法制备 球形超细镍粉"， 沈勇等， 化学通报， 1996年 1月）。 Shanghai East China University of Science and Technology has disclosed a method for preparing nickel powder with hydrazine hydrate as reducing agent, silver nitrate as nucleating agent and PVP as protective agent. The MS0 4 solution was directly added dropwise to a mixture containing Na 2 CO 3 , hydrazine hydrate and PVP (polyvinylpyrrolidone), and then AgN0 3 was added to nucleate. The nickel powder prepared by the method has a large particle size and a PVP dosage. Very large, high cost, and the formation of flake nickel during the reduction process (see, "Preparation of spherical superfine nickel powder by solution reduction method", Shen Yong Et al., Journal of Physical Chemistry, May 1996, Vol. 12, No. 5; and "Preparation of spherical ultrafine nickel powder by polymer protective solution reduction method", Shen Yong et al., Chemical Bulletin, January 1996).
JP8-246001公开了一种用 NiCl2蒸汽气相还原法制备的镍粉， 虽为高振实密度镍 粉， 但其粒径分布范围宽， 生产成本高， 而且设备投资极大， 不容易大规模地进行生 产。该方法需耗大量的加热能源，将 NiCl2在坩埚加热至 >900QC汽化温度，通过 Ar (氩) 气把汽化的 NiCl2蒸汽载入特定的反应容器中， 同时通入 H2气， 在给定温度下生成镍 粉。生成镍粉末在 Ar气的保护下送于冷却容器中间接冷却得产品。该方法的加热汽化、 H2反应容器、 冷却器均为特制设备， 要使用大量能耗和 Ar气惰性气体， 产能小， 成 本高。 发明内容 JP 8-246001 discloses a nickel powder prepared by a vapor phase reduction method using NiCl 2 , which is a high-shear density nickel powder, but has a wide particle size distribution range, high production cost, and great equipment investment, and is not easy to carry out on a large scale. produce. The method consumes a large amount of heating energy, and the NiCl 2 is heated to a vaporization temperature of >900 Q C in the crucible, and the vaporized NiCl 2 vapor is loaded into a specific reaction vessel through Ar (argon) gas, and H 2 gas is introduced at the same time. Nickel powder is produced at a given temperature. The resulting nickel powder is sent to the cooling vessel for indirect cooling under the protection of Ar gas. The heating vaporization, H 2 reaction vessel and cooler of the method are all special equipments, and a large amount of energy consumption and inert gas of Ar gas are used, and the productivity is small and the cost is high. Summary of the invention
本发明的目的在于克服以上不足，提供一种能大大降低生产成本，密度可与 NiCl2 蒸汽气相还原法相比拟， 而粒径分布范围又很窄， 能很容易大规模化生产的溶液还原 法制造高振实密度超微球形金属镍粉的方法。 The object of the present invention is to overcome the above deficiencies and to provide a solution reduction method which can greatly reduce the production cost, the density can be compared with the NiCl 2 vapor phase reduction method, and the particle size distribution range is narrow, which can be easily mass-produced. A method of high-vibration density ultra-fine spherical metallic nickel powder.
本发明提供一种高振实密度超微球形金属镍粉的湿法制造方法， 该方法包括以下 步骤：  The invention provides a wet manufacturing method of high-vibration density ultra-micro spherical metal nickel powder, the method comprising the following steps:
(1)硫酸镍溶液与氢氧化钠和碳酸钠的混合溶液反应生成氢氧化镍以及镍的碱式 (1) The reaction of nickel sulfate solution with a mixed solution of sodium hydroxide and sodium carbonate to form nickel hydroxide and a basic form of nickel
±卜 ±卜
(2)加入多元醇作为形貌控制剂， 并且加入钇盐作成核剂。  (2) Adding a polyol as a form controlling agent, and adding a cerium salt as a nucleating agent.
(3)在 PH为 8.5〜12.5， 温度为 40〜95°C条件下， 加入肼或肼的水合物， 还原氢 氧化镍和镍的碱式盐， 制得高振实密度的超微球形金属镍粉。  (3) At a pH of 8.5 to 12.5 and a temperature of 40 to 95 ° C, a hydrate of lanthanum or cerium is added to reduce the basic salt of nickel hydroxide and nickel to obtain a high-density ultra-spherical metallic nickel powder. .
上述的多元醇至少为丙三醇、 丁三醇、 丁四醇、 二甘醇中的一种， 也可采用其它 的多元醇。  The above polyol is at least one of glycerol, butyltriol, tetrabutylol and diethylene glycol, and other polyols may also be used.
和钇盐至少是硫酸钇、 硝酸钇、 氯化钇、 醋酸钇、 甲酸钇中的一种， 也可釆用其 它钇盐。  The barium salt is at least one of barium sulfate, barium nitrate, barium chloride, barium acetate, and barium formate, and other barium salts may also be used.
上述的多元醇的加入量为反应体系中镍重量的 10〜500%。  The above polyol is added in an amount of 10 to 500% by weight based on the weight of nickel in the reaction system.
上述的硫酸镍溶液的摩尔浓度为 0.1〜2.5mol/L。  The above nickel sulfate solution has a molar concentration of 0.1 to 2.5 mol/L.
上述的氢氧化钠 (NaOH)和碳酸钠 Na2C03混合液中的氢氧化钠 (NaOH)与碳酸钠 (Na2C03)的重量比为 0.2〜10： 1。 By weight of the sodium hydroxide (NaOH) and sodium carbonate Na 2 C0 3 in a mixture of sodium hydroxide (NaOH) and sodium carbonate (Na 2 C0 3) ratio of 0.2~10: 1.
上述的钇盐的用量为反应体系中镍重量的 0.0002〜0.2%。 ， 上述的肼或肼的水合物浓度为 10〜80% (重量百分比浓度)。 The above-mentioned barium salt is used in an amount of 0.0002 to 0.2% by weight based on the weight of nickel in the reaction system. , The above hydrazine or hydrazine has a hydrate concentration of 10 to 80% by weight.
上述硫酸镍的摩尔数： [(氢氧化钠的摩尔数) /2+碳酸钠的摩尔数]为 0.39至 0.94: 1。 所述的肼或肼的水合物与硫酸镍的摩尔比为 1.0至 2.0: 1。  The number of moles of the above nickel sulfate: [(moles of sodium hydroxide) / 2 moles of sodium carbonate] is 0.39 to 0.94:1. The molar ratio of the hydrazine or hydrazine hydrate to nickel sulfate is from 1.0 to 2.0:1.
本发明还提供一种由上面所述的方法制造的高振实密度超微球形金属镍粉。  The present invention also provides a high tap density ultrafine spherical metallic nickel powder produced by the method described above.
上述的高振实密度超微球形金属镍粉平均粒径为 0.2〜1.0μπι， 粒度分布为其平均 粒径的 ±60%, 且振实密度大于 3.9g/cm3。 附图说明 The above high-density ultrafine spherical metallic nickel powder has an average particle diameter of 0.2 to 1.0 μm, a particle size distribution of ±60% of its average particle diameter, and a tap density of more than 3.9 g/cm 3 . DRAWINGS
图 1为由实施例 4制备的高振实密度超微球形金属镍粉的电子显微镜照片。  BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an electron micrograph of a high tap density ultrafine spherical metallic nickel powder prepared in Example 4.
图 2为由实施例 4制备的高振实密度超微球形金属镍粉的粒径分布图。  Fig. 2 is a graph showing the particle size distribution of the high-shear density ultrafine spherical metallic nickel powder prepared in Example 4.
图 3为由实施例 3制备的高振实密度超微球形金属镍粉的电子显微镜照片。  Fig. 3 is an electron micrograph of the high tap density ultrafine spherical metallic nickel powder prepared in Example 3.
图 4为由实施例 3制备的高振实密度超微球形金属镍粉的粒径分布图。 具体实施方式  Fig. 4 is a graph showing the particle size distribution of the high-shear density ultrafine spherical metallic nickel powder prepared in Example 3. detailed description
本发明方法是用硫酸镍溶液与 NaOH和 Na2C03的混合溶液反应， 生成 M(OH)2 和 NiC03'Ni(OH)2沉淀， 加入多元醇和钇盐， 在 PH为 8.5〜12.5， 温度为 40〜95°C条 件下， 加入肼或肼的水合物， 还原 Ni(OH)2和 NiC03_Ni(OH)2， 制得平均粒径为 0.2〜 Ι.Ομιη可控的高振实密度的超微球形金属镍粉。 The method of the invention is to react a nickel sulfate solution with a mixed solution of NaOH and Na 2 CO 3 to form a precipitate of M(OH) 2 and NiC0 3 'Ni(OH) 2 , and add a polyol and a phosphonium salt at a pH of 8.5 to 12.5. At a temperature of 40 to 95 ° C, a hydrate of ruthenium or osmium is added to reduce Ni(OH) 2 and NiC0 3 _Ni(OH) 2 to obtain a high tap density with an average particle diameter of 0.2 Ι.Ομιη. Ultra micro spherical metal nickel powder.
本发明的特点在于还原体系中， 加入多元醇， 利用其良好的分散作用及特有的吸 附性质， 有效地阻止还原时生成镍粉的团聚。 同时使镍粉颗粒各个方向的生长趋于一 致， 从而使制造出的镍粉均勾性好， 表面光滑， 球形度好。再者， 钇盐成核剂的加入， 保证了氧化一还原反应顺利并稳定地进行， 同时也减弱了镍的,磁性， 从而使还原时镍 粉的生成更加致密， 因而得到高密度镍粉。  The present invention is characterized in that a polyhydric alcohol is added to the reduction system, and its good dispersion and unique adsorption properties are utilized to effectively prevent agglomeration of nickel powder during reduction. At the same time, the growth of the nickel powder particles in all directions tends to be uniform, so that the produced nickel powder has good hooking property, smooth surface and good sphericity. Furthermore, the addition of the cerium salt nucleating agent ensures that the oxidation-reduction reaction proceeds smoothly and stably, and at the same time, the nickel and magnetic properties are weakened, so that the formation of nickel powder during the reduction is more dense, thereby obtaining a high-density nickel powder.
本发明能制备出平均粒径为 0.2〜1μηι， 并且粒径可控的高振实密度， 球形规则的 金属镍粉，其振实密度大，表面光滑，氧化率低 (含氧量 <0.5%),抗氧化性强 (120〜140°C 在空气中放置 2小时含氧量不会增加)， 粒径分布范围窄， 如下表- 平均粒径 粒径分布 振实密度 比表面积 The invention can prepare a high-vibration density with an average particle diameter of 0.2~1μηι and a controllable particle size, and a spherical metal nickel powder having a large tap density, a smooth surface and a low oxidation rate (oxygen content <0.5%). Strong oxidation resistance (120~140°C does not increase oxygen content when placed in air for 2 hours), the particle size distribution range is narrow, as shown in the following table - Average particle size distribution, tap density, specific surface area
(μιη) (g/cm3) (m2/g) (μιη) (g/cm 3 ) (m 2 /g)
0.25 0.1-0.4 >4.0 <2.8  0.25 0.1-0.4 >4.0 <2.8
0.45 0.3-0.7 >4.5 <1.6  0.45 0.3-0.7 >4.5 <1.6
0.7 0.4-0.9 >4.6 <1.5  0.7 0.4-0.9 >4.6 <1.5
0.9 0.5-1.2 >4.8 <1.3 本发明可极大地减少环境污染， 设备投资少， 生产成本低， 适宜大工业化生产， 制造出的镍粉可广泛应用于多层陶瓷贴片电容器 (MLCC)、粉末冶金、磁性材料等行业。 本发明所使用的溶液为蒸馏水、 酸、 碱， 原材料为较纯工业品。 生产过程中， 无 COD 有机耗氧物排放； 母液可循环使用； 溢出微量含氨尾气抽入酸槽罐与硫酸反应生成硫 酸铵； 无粉尘、 废渣产生， 工艺运行对环境污染小。  0.9 0.5-1.2 >4.8 <1.3 The invention can greatly reduce environmental pollution, has low equipment investment, low production cost, and is suitable for large industrial production. The produced nickel powder can be widely used in multilayer ceramic chip capacitors (MLCC) and powders. Metallurgy, magnetic materials and other industries. The solution used in the present invention is distilled water, acid, and alkali, and the raw material is a relatively pure industrial product. In the production process, there is no COD organic oxygen consumption discharge; the mother liquor can be recycled; the overflow of trace ammonia-containing tail gas is pumped into the acid tank and reacted with sulfuric acid to form ammonium sulfate; no dust or waste residue is generated, and the process operation has little environmental pollution.
普通精细化工设备即可满足该发明工艺， 这区别于 "蒸汽气相物理法"或 "等离 子气相法"， 它们需大功率电加热、 惰性气体保护、 氢气还原等大量设备投资。  Ordinary fine chemical equipment can satisfy the invention process, which is different from "steam gas phase physical method" or "plasma gas phase method", which require a large amount of equipment investment such as high-power electric heating, inert gas protection, and hydrogen reduction.
以下， 本发明由非限制性实施例和比较进行更详细地举例说明， 但是这些实施例 并不限制本发明的范围。 实施例  In the following, the invention is illustrated in more detail by way of non-limiting examples and comparative examples, but these examples do not limit the scope of the invention. Example
本发明实施例和比较例中制备的镍粉的性质是通过下面的测试项目进行评估的。 1.粒径：  The properties of the nickel powder prepared in the examples and comparative examples of the present invention were evaluated by the following test items. 1. Particle size:
SEM法测试得到电子显微图像 (JSM-5900电子扫描显微镜，由日本 NEC株式会社 制造)， 测试条件为： 20KU, 10000〜20000放大倍数。  An electron microscopic image (JSM-5900 electronic scanning microscope, manufactured by NEC Corporation, Japan) was obtained by SEM test under the following conditions: 20 KU, 10000 to 20000 magnification.
2.粒径分布：  2. Particle size distribution:
由 DIP法 (Digital image processing)分析得到检测数据， 显微数字图像分析***为 JSM-5900电子显微镜配套软件。  The detection data is obtained by DIP method (Digital image processing), and the microscopic digital image analysis system is the supporting software of JSM-5900 electron microscope.
3.振实密度：  3. Tap density:
由 JZ-1振实密度测定仪 (中国 CDGX公司制造)测试得到数据。  The data was obtained by a JZ-1 tap density meter (manufactured by China CDGX Corporation).
4.氧含量- 由 TC-434氮氧测定仪 (美国 LECO公司制造)测试得到数据，测试条件为：样品 lg， 通入 He载气， 测定温度 3000°C， 测定时间 40秒。 4. Oxygen content - The data was obtained by TC-434 Nitrogen Analyzer (manufactured by LECO, USA). The test conditions were: sample lg, The He carrier gas was introduced, the temperature was measured at 3000 ° C, and the measurement time was 40 seconds.
5. 比表面积：  5. Specific surface area:
根据 BET 法测试得到数据 (ASAP-2010 自动吸附比表面测定仪， 由美国 Micromeritics公司制造)， 测试条件为： 样品 0.6g经 150QC和真空条件下脱气预处理 2 小时， 吸附介质为高纯氮气， 77.35K液氮温度下测定。 实施例 1 : According to the BET method test data (ASAP-2010 automatic adsorption specific surface measuring instrument, manufactured by Micromeritics, USA), the test conditions are: 0.6g of sample is degassed and pretreated for 2 hours under vacuum condition of 150 Q C, and the adsorption medium is high. Pure nitrogen, measured at 77.35K liquid nitrogen temperature. Example 1 :
在容积为 2000L的搪瓷反应釜中， 加入 1500L去离子水、 19.6公斤 NaOH和 3.8 公斤 Na2C03， 搅拌充分溶解， 然后边搅拌边加入 1.3mol/L的硫酸镍溶液 195L至 PH 值 12，再加入 15公斤丙三醇，继续搅拌 30分钟后开始升温至 70°C，再加入 44L 40% (重 量百分比浓度)的水合肼溶液和 0.03克成核剂硫酸钇进行还原反应， 反应时间为 30分 钟， 反应结束后经过滤、 洗涤、 真空干燥制得金属镍粉。 In a 2,000-liter enamel reactor, add 1500 L of deionized water, 19.6 kg of NaOH, and 3.8 kg of Na 2 C0 3 , stir well, and then add 195 L of 1.3 mol/L nickel sulfate solution to pH 12 with stirring. Add 15 kg of glycerol, continue stirring for 30 minutes, then start to raise the temperature to 70 ° C, and then add 44 L of 40% (% by weight) hydrazine hydrate solution and 0.03 g of nucleating agent barium sulfate for reduction reaction, the reaction time is 30 minutes. After the reaction, the metal nickel powder is obtained by filtration, washing and vacuum drying.
通过上述方法制得的镍粉在 20000倍电镜下观察为规则球形， '表面光滑， 平均粒 径为 0.9μιη， 粒径分布范围为 0.5〜1.2μπι， 振实密度为 4.85 g/cm3， 氧含量 0.28%， 比 表面积为 1.13 m2/g。 实施例 2: The nickel powder prepared by the above method was observed to have a regular spherical shape under a 20,000-fold electron microscope, and the surface was smooth, the average particle diameter was 0.9 μm, the particle size distribution range was 0.5 to 1.2 μm, and the tap density was 4.85 g/cm 3 . The content is 0.28%, and the specific surface area is 1.13 m 2 /g. Example 2:
在容积为 2000L的反应釜中， 加入 1500L去离子水、 20.8公斤 NaOH和 12公斤 Na2C03，搅拌充分溶解，然后边搅拌边加入 1.4mol/L的硫酸镍溶液 200L至 PH值 11.8， 再加入 17公斤丁三醇， 继续搅拌 20分钟后开始升温至 80°C， 再加入 60% (重量百分 比浓度)的水合肼 34L和 0.05克成核剂氯化钇进行还原， 反应时间为 30分钟， 反应结 束后经过滤、 洗涤、 真空干燥制得金属镍粉。 In a reactor with a volume of 2000 L, add 1500 L of deionized water, 20.8 kg of NaOH and 12 kg of Na 2 CO 3 , stir well, and then add 1.4 mol/L of nickel sulfate solution 200 L to a pH of 11.8 with stirring. 17 kg of butyl triol was added, stirring was continued for 20 minutes, and the temperature was raised to 80 ° C. Then, 60% (weight percent) of hydrazine hydrate 34 L and 0.05 g of a nucleating agent cesium chloride were added for reduction, and the reaction time was 30 minutes. After completion, the metal nickel powder is obtained by filtration, washing, and vacuum drying.
通过上述方法 ¾得的镍粉在 20000倍电镜下观察为规则球形， 表面光滑， 平均粒 径为 0.8μιη， 粒径分布范围为 0.5~1.2μηι， 振实密度为 4.7 g/cm3， 氧含量 0.37%, 比表 面积为 1.21 m2/g。 实施例 3: The nickel powder obtained by the above method was observed to have a regular spherical shape under a 20,000-fold electron microscope, the surface was smooth, the average particle diameter was 0.8 μm, the particle size distribution range was 0.5 to 1.2 μηι, the tap density was 4.7 g/cm 3 , and the oxygen content was obtained. 0.37%, specific surface area is 1.21 m 2 /g. Example 3:
在容积为 2000L的反应釜中，加入 1500L去离子水、 24.5公斤 NaOH和 25.2公斤 Na2C03, 搅拌充分溶解后， 取 0.05克硫酸钇加入 200L 1.7mol/L的硫酸镍溶液中， 然 后边搅拌边把硫酸镍溶液往 NaOH、 Na2C03混合溶液中加至 PH值 11.7，再加入 10公 斤二甘醇，继续搅拌 20分钟后开始升温至 90°C,再加入 40% (重量百分比浓度)的水合 肼 60L进行还原， 30分钟反应结束， 经过滤、 洗涤， 真空干燥制得平均粒径为 0.7μπι 的金属镍粉。 （参见图 3和 4)， 其球形度好， 表面光滑， 粒径分布窄， 振实密度为 4.65 g/cm3， 氧含量 0.38%， 比表面积为 1.28 m2/g。 实施例 4: . In a reactor with a volume of 2000L, add 1500L of deionized water, 24.5kg of NaOH and 25.2kg of Na 2 C0 3 , stir well and then add 0.05g of barium sulfate to 200L of 1.7mol/L nickel sulfate solution, then Add the nickel sulfate solution to the NaOH and Na 2 C0 3 mixed solution to a pH of 11.7 while stirring, and then add 10 metrics. Ginger diethylene glycol, after stirring for 20 minutes, the temperature is raised to 90 ° C, and then 40% (weight percent) of hydrazine hydrate 60 L is added for reduction, and the reaction is finished for 30 minutes. After filtration, washing and vacuum drying, the average particle diameter is obtained. Metal nickel powder of 0.7 μm. (See Figures 3 and 4), the sphericity is good, the surface is smooth, the particle size distribution is narrow, the tap density is 4.65 g/cm 3 , the oxygen content is 0.38%, and the specific surface area is 1.28 m 2 /g. Example 4: .
在容积为 2000L的反应釜中， 加入 1500L去离子水、 25公斤 NaOH和 33.1公斤 Na2C03，搅拌充分溶解，然后边搅拌边加入 1.8mol/L的硫酸镍溶液 200L至 PH值 11.5， 再加入 15公斤丁四醇， 继续搅拌 20分钟后开始升温至 90°C， 再加入 80% (重量百分 比浓度)的水合肼 32L和 0.07克硫酸钇进行还原， 20分钟反应结束。 经过滤、 洗涤、 真空干燥制得平均粒径为 0.45μηι的光滑球形金属镍粉 (参见图 1和 2)，振实密度为 4.6 g/cm3, 氧含量 0.46%， 比表面积 1.48 m2/g。 实施例 5: In a reactor with a volume of 2000 L, add 1500 L of deionized water, 25 kg of NaOH and 33.1 kg of Na 2 CO 3 , stir well to dissolve, and then add 1.8 mol/L of nickel sulfate solution 200 L to a pH of 11.5 with stirring. After adding 15 kg of butyltetraol, stirring was continued for 20 minutes, and the temperature was raised to 90 ° C, and then 80% (weight percent) of hydrazine hydrate 32 L and 0.07 g of barium sulfate were added for reduction, and the reaction was terminated in 20 minutes. After filtering, washing and vacuum drying, a smooth spherical metallic nickel powder having an average particle diameter of 0.45 μm (see Figs. 1 and 2) was obtained, and the tap density was 4.6 g/cm 3 , the oxygen content was 0.46%, and the specific surface area was 1.48 m 2 / g. Example 5:
在容积为 2000L的反应釜中， 加入 1500L去离子水、 28公斤 NaOH和 17.4公斤 In a 2000L reactor, add 1500L of deionized water, 28kg of NaOH and 17.4kg.
Na2C03, 充分溶解后边搅拌边加入 2.0mol/L的硫酸镍溶液 200L至 PH值 11.4， 再加 入 30公斤丙三醇， 继续搅拌 20分钟后开始升温至 80°C， 再加入 40% (重量百分比浓 度)的水合肼 65L和 0.08硫酸钇进行还原， 20分钟反应结束。 经过滤、 洗涤、 真空干 燥制得平均粒径为 0.45μηι的金属镍粉，其球形度好，表面光滑，振实密度为 4.5 g/cm3, 粒径分布范围为 0.3μη！〜 0.9μηι， 比表面积 1.45 m2/g， 氧含量为 0.51%。 从中取 20克 样在暴露于空气之中的条件下， 置于 102-140°C的恒温普通烘箱中， 放置 2小时， 然 后取出测得氧含量为 0.51%。 实施例 6: Na 2 C0 3 , fully dissolved, and then add 2.0L of 2.0 mol/L nickel sulfate solution to a pH of 11.4, and then add 30 kg of glycerol. After stirring for 20 minutes, the temperature is raised to 80 ° C, and then 40% ( 5% by weight of hydrazine hydrate and 0.08 barium sulphate were reduced and the reaction was completed in 20 minutes. After filtering, washing and vacuum drying, the metal nickel powder with an average particle diameter of 0.45 μηι is obtained, the sphericity is good, the surface is smooth, the tap density is 4.5 g/cm 3 , and the particle size distribution range is 0.3 μηη! ~ 0.9μηι, specific surface area 1.45 m 2 /g, oxygen content 0.51%. 20 g of the sample was placed in a constant temperature ordinary oven at 102-140 ° C for 2 hours, and then the measured oxygen content was 0.51%. Example 6
在容积为 2000L的反应釜中， 加入 1400L去离子水、 42公斤丙三醇、 32.4公斤 In a reactor with a volume of 2000 L, add 1400 L of deionized water, 42 kg of glycerol, 32.4 kg.
NaOH和 84.4公斤 Na2C03， 充分溶解后边搅拌边加入 2.3mol/L的硫酸镍溶液 206L 至 PH值 11，继续搅拌 20分钟后开始升温至 90°C，再加入 60% (重量百分比浓度)的水 合肼 56L和 0.1克硫酸钇进行还原， 20分钟反应结束。 经过滤、 洗涤、 真空干燥制得 平均粒径为 0.25μπι的金属镍粉， 经 20000倍电镜观察， 其球形度好， 表面光滑， 振实 密度为 4.1 g/cm3,粒径分布范围为 Ο.ΐμπ！〜 0.4μηι，氧含量 0.58%，比表面积 2.73 m2/g。 在容积为 2000L的反应釜中， 加入 1400L去离子水、 140公斤丙三醇、 16.5公斤 NaOH和 82.5公斤 Na2C03, 充分溶解后边搅拌边加入 2.5mol/L的硫酸镍溶液 206L 至 PH值 8.5， 继续搅拌 20分钟后开始升温至 40°C， 再加入 60% (重量百分比浓度)的 水合肼 60L和 59克硫酸钇进行还原， 40分钟反应结束。 经过滤、 洗涤、 真空干燥制 得平均粒径为 0.20μιη的金属镍粉， 经 20000倍电镜观察， 其球形度好， 表面光滑， 振 实密度为 3.9 g/cm3， 粒径分布范围为 Ο.ΐμη！〜 0.35μπι， 氧含量 0.72%， 比表面积 2.95 m 实施例 8: NaOH and 84.4 kg of Na 2 C0 3 , fully dissolved, and then add 2.3 mol/L of nickel sulfate solution 206L to pH 11 with stirring. After stirring for 20 minutes, the temperature is raised to 90 ° C, and then 60% (weight percent concentration) is added. The hydrazine hydrate 56L and 0.1 gram of barium sulphate were reduced, and the reaction was completed in 20 minutes. After filtering, washing and vacuum drying, the metal nickel powder with an average particle diameter of 0.25 μm was obtained. After 20,000 times electron microscope observation, the sphericity was good, the surface was smooth, the tap density was 4.1 g/cm 3 , and the particle size distribution range was Ο. .ΐμπ! ~ 0.4μηι, oxygen content 0.58%, specific surface area 2.73 m 2 /g. In a reactor with a volume of 2000 L, add 1400 L of deionized water, 140 kg of glycerol, 16.5 kg of NaOH and 82.5 kg of Na 2 C0 3 , fully dissolved, and then add 2.5 mol/L of nickel sulfate solution 206 L to the pH value while stirring. 8.5. After stirring for 20 minutes, the temperature was raised to 40 ° C, and 60% (weight percent) of hydrazine hydrate 60 L and 59 g of barium sulfate were added for reduction, and the reaction was completed for 40 minutes. After filtering, washing and vacuum drying, the metal nickel powder with an average particle diameter of 0.20μηη was obtained. After 20,000 times electron microscope observation, the sphericity was good, the surface was smooth, the tap density was 3.9 g/cm 3 , and the particle size distribution range was Ο. .ΐμη! ~ 0.35μπι, oxygen content 0.72%, specific surface area 2.95 m Example 8:
在容积为 2000L的反应釜中， 加入 1400L去离子水、 100公斤丙三醇、 20公斤 NaOH和 80.5公斤 Na2C03， 充分溶解后边搅拌边加入 2.3mol/L的硫酸镍溶液 206L 至 PH值 9.0， 继续撹拌 20分钟后开始升温至 60°C， 再加入 60% (重量百分比浓度)的 水合肼 55L和 3.0克硫酸钇进行还原， 40分钟反应结束。 经过滤、 洗涤、 真空干燥制 得平均粒径为 0.22μιη的金属镍粉， 经 20000倍电镜观察， 其球形度好， 表面光滑， 振 实密度为 4.0 g/cm3, 粒径分布范围为 Ο.ΐμπ！〜 0.4μπι， 氧含量 0.68%， 比表面积 2.86 m 比较例 1 : In a reactor with a volume of 2000 L, add 1400 L of deionized water, 100 kg of glycerol, 20 kg of NaOH and 80.5 kg of Na 2 C0 3 , fully dissolved, and then add 2.3 mol/L of nickel sulfate solution 206 L to the pH while stirring. 9.0. After the mashing was continued for 20 minutes, the temperature was raised to 60 ° C, and then 60% (weight percent) of hydrazine hydrate 55 L and 3.0 g of barium sulfate were added for reduction, and the reaction was completed in 40 minutes. After filtering, washing and vacuum drying, the metal nickel powder with an average particle diameter of 0.22μηη was obtained. After 20,000 times electron microscope observation, the sphericity was good, the surface was smooth, the tap density was 4.0 g/cm 3 , and the particle size distribution range was Ο. .ΐμπ! ~ 0.4μπι, oxygen content 0.68%, specific surface area 2.86 m Comparative Example 1:
在容积为 2000L的搪瓷反应釜中， 加入 1500L去离子水、 19.6公斤 NaOH， 搅拌 充分溶解， 然后边搅拌边加入 1.3mol/L的硫酸镍溶液 195L至 PH值 12， 再加入 15公 斤丙三醇， 继续搅拌 30分钟后开始升温至 70°C， 再加入 44L 40% (重量百分比浓度) 的水合肼溶液和 0.03克成核剂硫酸钇进行还原反应， 反应时间为 30分钟， 反应结束 后经过滤、 洗涤、 真空干燥制得金属镍粉。  In a 2,000-liter enamel reactor, add 1500 L of deionized water, 19.6 kg of NaOH, stir well to dissolve, then add 195 L of 1.3 mol/L nickel sulfate solution to pH 12 with stirring, and then add 15 kg of glycerol. After stirring for 30 minutes, the temperature was raised to 70 ° C, and then 44 L of a 40% (by weight concentration) hydrazine hydrate solution and 0.03 g of a nucleating agent barium sulfate were added to carry out a reduction reaction for 30 minutes. After the reaction, the solution was filtered. The metal nickel powder is obtained by washing and vacuum drying.
通过上述方法制得的镍粉在 20000倍电镜下观察为类球形， 表面毛剌状， 平均粒 径为 0.9μιη， 粒径分布范围为 0.3〜2.5μηι， 振实密度为 2.5 g/cm3, 氧含量 1.28%， 比 表面积为 8.26 m2/g。 比较例 The nickel powder prepared by the above method is spherical under the electron microscope of 20,000 times, has a surface-like shape, an average particle diameter of 0.9 μm, a particle size distribution range of 0.3 to 2.5 μηι, and a tap density of 2.5 g/cm 3 . The oxygen content was 1.28% and the specific surface area was 8.26 m 2 /g. Comparative example
7 在容积为 2000L的搪瓷反应釜中， 加入 1500L去离子水、 19.6公斤 NaOH和 1.96 公斤 Na2C03， 搅拌充分溶解， 然后边搅拌边加入 1.3mol/L的硫酸镍溶液 195L至 PH 值 12.5, 再加入 15公斤丙三醇， 继续搅拌 30分钟后开始升温至 95°C, 再加入 44L 40% (重量百分比浓度)的水合肼溶液和 0.15克成核剂硫酸钇进行还原反应， 反应时间 为 30分钟， 反应结束后经过滤、 洗涤、 真空干燥制得金属镍粉。 7 In a 2000 L enamel autoclave, add 1500 L of deionized water, 19.6 kg of NaOH and 1.96 kg of Na 2 C0 3 , stir well, and then add 195 L of 1.3 mol/L nickel sulfate solution to a pH of 12.5 with stirring. Add 15 kg of glycerol, continue stirring for 30 minutes, then start to raise the temperature to 95 ° C, then add 44 L of 40% (% by weight) hydrazine hydrate solution and 0.15 g of nucleating agent barium sulfate for reduction reaction, the reaction time is 30 minutes. After the reaction, the metal nickel powder is obtained by filtration, washing and vacuum drying.
通过上述方法制得的镍粉在 20000倍电镜下观察为规则球形， 表面光滑， 平均粒 径为 Ι.Ομηι, 粒径分布范围为 0.5〜1.3μη， 振实密度为 4.5 g/cm3, 氧含量 0.38%， 比 表面积为 1.25 m2/g。 比较例 3 : The nickel powder prepared by the above method is observed to have a regular spherical shape under a 20,000-fold electron microscope, and has a smooth surface, an average particle diameter of Ι.Ομηι, a particle size distribution range of 0.5 to 1.3 μη, a tap density of 4.5 g/cm 3 , and oxygen. The content is 0.38% and the specific surface area is 1.25 m 2 /g. Comparative Example 3:
在容积为 2000L的反应釜中， 加入 1500L去离子水、 20.8公斤 NaOH和 12公斤 Na2C03,搅拌充分溶解，然后边搅拌边加入 1.4mol/L的硫酸镍溶液 200L至 PH值 11.8， 继续搅拌 20分钟后开始升温至 80°C， 再加入 60% (重量百分比浓度)的水合肼 34L和 0.05克成核剂氯化钇进行还原， 反应时间为 30分钟， 反应结束后经过滤、洗涤、真空 干燥制得金属镍粉。 In a reactor with a volume of 2000 L, add 1500 L of deionized water, 20.8 kg of NaOH and 12 kg of Na 2 CO 3 , stir well, and then add 1.4 mol/L of nickel sulfate solution 200 L to a pH of 11.8 while stirring. After stirring for 20 minutes, the temperature was raised to 80 ° C, and then 60% (weight percent) of hydrazine hydrate 34 L and 0.05 g of nucleating agent cesium chloride were added for reduction, the reaction time was 30 minutes, and the reaction was filtered, washed, and vacuumed. Drying to produce metallic nickel powder.
通过上述方法制得的镍粉在 20000倍电镜下观察为类球形， 表面不光滑， 平均粒 径为 0.82μιη， 粒径分布范围为 0.4〜1.8μιη， 振实密度为 2.8 g/cm3, 氧含量 1.32%， 比 表面积为 5.63 m2/g。 比较例 4: The nickel powder prepared by the above method is spherical under the electron microscope of 20,000 times, the surface is not smooth, the average particle diameter is 0.82 μιη, the particle size distribution range is 0.4 to 1.8 μιη, the tap density is 2.8 g/cm 3 , oxygen The content was 1.32% and the specific surface area was 5.63 m 2 /g. Comparative Example 4:
在容积为 2000L的反应釜中，加入 1500L去离子水、 24.5公斤 NaOH和 25.2公斤 Na2C03, 搅拌充分溶解后， 加入 200L 1.7mol/L的硫酸镍溶液至. PH值 11.7， 再加入 10公斤二甘醇， 继续搅拌 20分钟后开始升温至 90°C， 再加入 40% (重量百分比浓度) 的水合肼 60L进行还原， 60分钟反应结束， 经过滤、 洗涤， 真空干燥制得平均粒径为 0.7μηι的金属镍粉， 其为类球形， 表面不光滑， 粒径分布方范围为 0.4-2.3 μπι， 振实密 度为 3.8 g/cm3， 氧含量 0.82%， 比表面积为 2.5 m2/g。 上述各实施例是对本发明的进一步说明， 但不应将此理解为本发明的范围仅限于 上述实施例。 本领域的普通技术人员应当理解的是可以在其中进行形式和细节的各种 变化， 而没有离开本发明由后附权利要求定义的精神和范围。 In a reactor with a volume of 2000 L, add 1500 L of deionized water, 24.5 kg of NaOH and 25.2 kg of Na 2 C0 3 , stir well, then add 200 L of 1.7 mol/L nickel sulfate solution to a pH of 11.7, then add 10 Kilogram of diethylene glycol, continue to stir for 20 minutes, then start to raise the temperature to 90 ° C, then add 40% (weight percent) of hydrazine hydrate 60L for reduction, 60 minutes of reaction is finished, filtered, washed, vacuum dried to obtain the average particle size Metal nickel powder of 0.7μηι, which is spherical like, has a non-smooth surface, a particle size distribution range of 0.4-2.3 μπι, a tap density of 3.8 g/cm 3 , an oxygen content of 0.82%, and a specific surface area of 2.5 m 2 / g. The above embodiments are further illustrative of the invention, but it should not be construed that the scope of the invention is limited to the embodiments described above. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1、 一种高振实密度超微球形金属镍粉的湿法制造方法， 该方法包括以下步骤： A wet manufacturing method for a high-vibration density ultrafine spherical metal nickel powder, the method comprising the steps of:
(1)硫酸镍溶液与氢氧化钠和碳酸钠的混合溶液反应生成氢氧化镍以及镍的碱式(1) The reaction of nickel sulfate solution with a mixed solution of sodium hydroxide and sodium carbonate to form nickel hydroxide and a basic form of nickel
±卜 ±卜
(2)加入多元醇作为形貌控制剂， 并且加入钇盐作成核剂。  (2) Adding a polyol as a form controlling agent, and adding a cerium salt as a nucleating agent.
(3)在 PH为 8.5〜12.5， 温度为 40〜95°C条件下， 加入肼或肼的水合物， 还原氢 权  (3) Adding hydrazine or hydrazine hydrate to reduce the hydrogen weight at a pH of 8.5 to 12.5 and a temperature of 40 to 95 °C.
氧化镍和镍的碱式盐， 制得高振实密度的超微球形金属镍粉。 A basic salt of nickel oxide and nickel produces an ultrafine spherical metallic nickel powder having a high tap density.
2、如权利要求 1所述的高振实密度超微球形金属镍粉的湿法制造方法， 其中， 所 述的多元醇至少为丙三醇、 丁三醇、 丁四醇、 二甘醇中的一种。  The method for wet-fabricating high-density ultra-fine spherical metallic nickel powder according to claim 1, wherein the polyol is at least one of glycerol, butyl alcohol, butyl alcohol, and diethylene glycol. Kind.
求  begging
3、如权利要求 1所述的高振实密度超微球形金属镍粉的湿法制造方法， 其中， 所 述的钇盐至少是硫酸钇、 硝酸钇、 氯化钇、 醋酸钇、 甲酸钇中的一种。  The method for wet-fabricating high-density ultra-fine spherical metallic nickel powder according to claim 1, wherein the cerium salt is at least one of barium sulfate, cerium nitrate, cerium chloride, cerium acetate, cerium formate. Kind.
4、如权利要求 1至 3任何一项所述的高振实密度超微球形金属镍粉的湿法制造方 法， 其中所述多元醇的加入量为反应体系中镍重量的 10〜500%。  The wet-fabrication method of a high-vibration density ultrafine spherical metallic nickel powder according to any one of claims 1 to 3, wherein the polyol is added in an amount of from 10 to 500% by weight based on the weight of nickel in the reaction system.
5、如权利要求 1至 3任何一项所述的高振实密度超微球形金属镍粉的湿法制造方 法， 其中， 硫酸镍的摩尔数： [(氢氧化钠的摩尔数) /2+碳酸钠的摩尔数]为 0.39至 0.94: 1。  The wet-fabrication method of high-vibration density ultrafine spherical metal nickel powder according to any one of claims 1 to 3, wherein the number of moles of nickel sulfate: [(moles of sodium hydroxide) / 2+ sodium carbonate The number of moles] is from 0.39 to 0.94: 1.
6、如权利要求 1至 3任何一项所述的高振实密度超微球形金属镍粉的湿法制造方 法， 其中， 所述氢氧化钠和碳酸钠混合液中， 氢氧化钠与碳酸钠的重量比为 0.2〜10： 1。  The wet-fabrication method of a high-vibration density ultrafine spherical metal nickel powder according to any one of claims 1 to 3, wherein the weight of sodium hydroxide and sodium carbonate in the sodium hydroxide and sodium carbonate mixture is The ratio is 0.2~10: 1.
7、如权利要求 1至 3任何一项所述的高振实密度超微球形金属镍粉的湿法制造方 法， 其中， 所述的钇盐的用量为反应体系中镍重量的 0.0002〜0.2%。  The wet-fabrication method of a high-vibration density ultrafine spherical metallic nickel powder according to any one of claims 1 to 3, wherein the cerium salt is used in an amount of 0.0002 to 0.2% by weight based on the weight of nickel in the reaction system.
8、如权利要求 1至 3任何一项所述的高振实密度超微球形金属镍粉的湿法制造方 法， 其中， 所述的肼或肼的水合物与硫酸镍的摩尔比为 1.0至 2.0: 1。  The wet-fabrication method of a high-vibration density ultrafine spherical metal nickel powder according to any one of claims 1 to 3, wherein the molar ratio of the ruthenium or osmium hydrate to nickel sulfate is from 1.0 to 2.0: 1.
9、一种由权利要求 1至 8任何一项所述的高振实密度超微球形金属镍粉的湿法制 造方法制造的高振实密度超微球形金属镍粉。  A high-shear density ultrafine spherical metallic nickel powder produced by the wet process for producing high-vibration ultra-fine spherical metallic nickel powder according to any one of claims 1 to 8.
10、 如权利要求 9所述的高振实密度超微球形金属镍粉， 其平均粒径为 0.2〜 Ι.Ομπι, 粒度分布为其平均粒径的 ±60%, 且振实密度大于 3.9g/cm3。 10. The high-vibration density ultrafine spherical metallic nickel powder according to claim 9, which has an average particle diameter of 0.2 to Ο.Ομπι, a particle size distribution of ±60% of its average particle diameter, and a tap density of more than 3.9 g/cm. 3 .
PCT/CN2005/001861 2004-12-28 2005-11-07 Spherical ultrafine nickel powder with high tap density and its wet processes preparing mothod WO2006069513A1 (en)

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