WO2011131008A1 - Method for preparing nano-nickel powder with microchannel reactor - Google Patents
Method for preparing nano-nickel powder with microchannel reactor Download PDFInfo
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- WO2011131008A1 WO2011131008A1 PCT/CN2010/079476 CN2010079476W WO2011131008A1 WO 2011131008 A1 WO2011131008 A1 WO 2011131008A1 CN 2010079476 W CN2010079476 W CN 2010079476W WO 2011131008 A1 WO2011131008 A1 WO 2011131008A1
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- nickel
- microchannel reactor
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 title claims abstract description 17
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229930182558 Sterol Natural products 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 150000003432 sterols Chemical class 0.000 claims description 4
- 235000003702 sterols Nutrition 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 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 2
- 239000000243 solution Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 239000002270 dispersing agent Substances 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 3
- 230000001476 alcoholic effect Effects 0.000 abstract 2
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- B22F9/24—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
- 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 relates to a preparation method of preparing nano metal nickel powder, in particular to a method for continuously preparing nano nickel powder through a microchannel reactor. Background technique
- Nanomaterials are one of the most active areas of current research. Due to their unique physical and chemical properties, nano-nickel has been widely used in many fields such as catalysts, battery materials, magnetic materials and nano-coating materials.
- the preparation methods of nano nickel mainly include a carboxyl group thermal decomposition method, an evaporation condensation method, a physical preparation method, a hydrothermal method, an electrolysis method, a mechanical pulverization method, a microemulsion method, and a chemical reduction method.
- the liquid phase chemical reduction method has become a focus of researchers due to its advantages such as simple process, easy operation, and uniform product particles.
- Patent CN200510121349.1 discloses a preparation method of nano nickel powder, which uses water-soluble polymer monomer as surface dispersant, hydrazine hydrate or sodium borohydride as reducing agent, and uses a batch reactor to liquid phase under alkaline conditions.
- Nano nickel powder having a particle diameter of 10 to 50 nm was prepared by reducing nickel chloride or nickel sulfate.
- Patent CN200810123127.7 uses sodium disulfite as reducing agent, polyvinylpyrrolidone as dispersant, propylene glycol-water mixed solution as reaction medium, and nano-nickel powder with particle size of 30-60 nm synthesized by liquid phase chemical reduction in batch reactor. .
- the method has simple process, low production cost and good industrial application prospect.
- Patent CN200910051160.8 In the preparation of nano-nickel powder, the nickel salt and the dispersing agent are thoroughly mixed, and then the alkali solution is added dropwise, and after stirring for 30-60 minutes, the reducing agent is added dropwise to carry out the reduction reaction.
- the nano nickel powder is uniformly dispersed and the preparation process is simple.
- Patent CN03113326.6 discloses a process and a special equipment for continuously preparing ultrafine nano powder by a precipitation method, which first mixes a nickel salt and a reducing agent in a tank reactor, and then mixes the materials. The reaction is carried out in a tubular reactor equipped with a static mixer, and finally a nano-nickel powder having a good dispersibility and a narrow particle size distribution can be obtained.
- the whole process is continuous and simple to operate, but conventional reactors have different degrees of "magnification effect" during the amplification process.
- microchannel reactors have achieved remarkable results in the continuous preparation of nano metal particles due to their excellent properties in heat transfer, mass transfer, size control and absence of "amplification effect". Microchannels have been successfully utilized.
- the reactor continuously synthesizes a variety of nano metal particles, including Au (Nano Lett. 2005, 5, 685), Ag (Nano Lett. 2004, 4, 2227), Pt (J. Nanosci. Nanotechnol. 2004, 4, 788), Cu (J. Phys. Chem. B. 2005, 109, 9330) and Co (Chem. Mater.
- the object of the present invention is to overcome the disadvantages of low batch production efficiency, and to utilize the flow form of the gas-liquid two-phase block flow formed by partial vaporization of the solvent to solve the problem of clogging of the microchannel during the synthesis of the particles, and to provide a A method for preparing nano-nickel powder using a microchannel reactor.
- the technical scheme of the invention is: A method for preparing nano nickel powder by using a microchannel reactor, the specific steps are:
- liquid A and the liquid B are mixed according to the molar ratio of hydrazine hydrate/nickel ion 2 ⁇ 10:1 by pump into the heated micro-mixer, and the mixed liquid is directly injected into the heated microchannel reactor to collect and collect. Discharge product;
- the soluble nickel salt is nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, more preferably nickel chloride or nickel acetate; and the concentration of the alcohol solution of the soluble nickel salt is 0.05 to 1.0 mol/L.
- Step 1) The concentration of the alkali-containing hydrazine hydrate solution in the B solution is 0.15-2 mol/L, and the molar ratio of the alkali/hydrated hydrazine is 0.8 to 1.2:1.
- the base in the alkali-containing hydrazine hydrate solution in the step 1) is NaOH or KOH; preferably the alcohol in the solution A and the solution B in the step 1) is methanol, ethanol, isopropanol or ethylene glycol, more preferably methanol, Ethanol.
- the micro-mixer and the micro-channel reactor are heated at a temperature of 50 to 90 V.
- the micromixer has a channel diameter of 25 to 200 ⁇ m
- the material stays in the micromixer for 10 to 100 ms
- the microchannel reactor has an inner diameter of 0.5 to 3 mm
- the residence time of the material in the microchannel reactor is 2 ⁇ 30 min.
- the invention adopts a microchannel reactor for nano nickel synthesis, which can realize continuous and controllable reaction process, and is simple and easy to operate, has no "amplification effect", and the production process can be industrialized;
- the invention does not add any other dispersing agent or initiator in the synthesis process, and the raw material cost is low, and the synthesized nano nickel particles have the advantages of narrow particle size distribution and good dispersibility;
- the invention adopts a partial vaporization of a solvent to form a gas-liquid two-phase block flow, which can avoid the nano-particles in the micro-pass Blockage in the channel and facilitate subsequent separation of the product.
- FIG. 1 is a schematic flow chart of a device for preparing a nano-nickel powder in a microchannel reactor, wherein a: a nickel salt alcohol solution; b: a hydration sterol solution containing a base; 1-1 and 1-2: a feed pump; 2: a micromixer 3: water bath heating constant temperature zone; 4: microchannel reactor; 5: product collection tank;
- Example 2 is an X-ray diffraction pattern (XRD) of the sample of Example 1;
- Figure 3 is a transmission electron micrograph (TEM) of the sample of Example 1;
- Figure 4 is a field emission scanning electron micrograph (FESEM) of the sample of Example 2.
- the XRD shows that the sample is nickel metal, and the obtained nano nickel has an average particle diameter of 65 nm.
- the FESEM image of the sample is shown in Fig. 4.
- the feed was directly injected into the microchannel reactor (purchased from Nanjing Nianqing Industrial Co., Ltd.) with a reaction temperature of 62 °C and an internal diameter of 1 mm for 7 min to carry out the reaction.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
A method for preparing nano-nickel powder with microchannel reactor is provided. The method comprises the following steps: preparing the alcoholic solution of soluble nickel salt and the alcoholic solution of alkaliferous hydrazine hydrate; injecting the two solutions into a heated micromixer according to a certain molar ratio of hydrazine hydrate/nickel; directly injecting the mixed solution into the heated microchannel reactor; separating and washing the products and then storing them without air. During the preparation process, solvents partially vaporize to form a flowing form of gas phase and liquid phase section flows, which can eliminate the blockage in the microchannel reactor during the process of synthesizing the nano granules, and thereby the nano-nickel granules can be continuously synthesized. Furthermore, the preparation process has the advantages of no addition of any surfactants such as dispersing agents, low cost of raw materials, simple operation, uniform nano-nickel granule size, good dispersibility and the like.
Description
说明书 一种利用微通道反应器制备纳米镍粉的方法 Method for preparing nano nickel powder by using microchannel reactor
技术领域 Technical field
本发明涉及一种制备纳米金属镍粉的制备方法,尤其涉及一种通过微通道反应器连续 制备纳米镍粉的方法。 背景技术 The invention relates to a preparation method of preparing nano metal nickel powder, in particular to a method for continuously preparing nano nickel powder through a microchannel reactor. Background technique
纳米材料是当前研究最为活跃的领域之一, 纳米镍由于具备独特的物理和化学性质, 在催化剂、 电池材料、 磁性材料以及纳米涂层材料等许多领域得到了广泛应用。 Nanomaterials are one of the most active areas of current research. Due to their unique physical and chemical properties, nano-nickel has been widely used in many fields such as catalysts, battery materials, magnetic materials and nano-coating materials.
目前纳米镍的制备方法主要有羧基热分解法、蒸发冷凝法、物理制备法、水热法、 电 解法、机械粉碎法、微乳液法和化学还原法。在这些制备方法当中, 液相化学还原法由于 工艺简单、 便于操作、 产品颗粒均匀等优点成为研究人员关注的重点。 专利 CN200510121349.1公开了一种纳米镍粉的制备方法, 该方法以水溶性高分子单体为表面 分散剂,水合肼或硼氢化钠为还原剂,采用间歇反应器在碱性条件下液相还原氯化镍或硫 酸镍,制备了粒径为 10-50 nm的纳米镍粉。专利 CN200810123127.7以二亚硫酸钠为还原 剂, 聚乙烯吡咯烷酮为分散剂, 丙二醇 -水混合溶液为反应介质, 在间歇反应器中采用液 相化学还原法合成了粒径 30-60 nm的纳米镍粉。 该方法工艺过程简单、 生产成本低廉, 具有很好的工业应用前景。 专利 CN200910051160.8在制备纳米镍粉时, 先将镍盐和分散 剂充分混合,然后以滴加的方式加入碱液,搅拌 30-60 min后再滴加还原剂进行还原反应, 该方法获得的纳米镍粉分散均匀, 制备工艺简单。 At present, the preparation methods of nano nickel mainly include a carboxyl group thermal decomposition method, an evaporation condensation method, a physical preparation method, a hydrothermal method, an electrolysis method, a mechanical pulverization method, a microemulsion method, and a chemical reduction method. Among these preparation methods, the liquid phase chemical reduction method has become a focus of researchers due to its advantages such as simple process, easy operation, and uniform product particles. Patent CN200510121349.1 discloses a preparation method of nano nickel powder, which uses water-soluble polymer monomer as surface dispersant, hydrazine hydrate or sodium borohydride as reducing agent, and uses a batch reactor to liquid phase under alkaline conditions. Nano nickel powder having a particle diameter of 10 to 50 nm was prepared by reducing nickel chloride or nickel sulfate. Patent CN200810123127.7 uses sodium disulfite as reducing agent, polyvinylpyrrolidone as dispersant, propylene glycol-water mixed solution as reaction medium, and nano-nickel powder with particle size of 30-60 nm synthesized by liquid phase chemical reduction in batch reactor. . The method has simple process, low production cost and good industrial application prospect. Patent CN200910051160.8 In the preparation of nano-nickel powder, the nickel salt and the dispersing agent are thoroughly mixed, and then the alkali solution is added dropwise, and after stirring for 30-60 minutes, the reducing agent is added dropwise to carry out the reduction reaction. The nano nickel powder is uniformly dispersed and the preparation process is simple.
以上报道的液相化学还原法制备纳米镍粉均采用间歇方式合成,并通过在制备过程中 添加分散剂来阻止纳米镍的团聚, 这为后续处理带来了不便。专利 CN03113326.6公开了一 种采用沉淀法连续制备超细纳米粉体的工艺及专用设备,该工艺先将镍盐和还原剂等先在 釜式反应器中进行混合,然后将混合后的物料输送入配有静态混合器的管式反应器中进行 反应, 最终可以获得分散性好, 粒径分布窄的纳米镍粉。 整个工艺过程连续、 操作简单, 但是常规反应器在放大的过程中都会存在不同程度的 "放大效应"。 近年来, 微通道反应 器由于在传热、 传质、 尺寸控制及不存在 "放大效应"等方面的优异特性, 在连续制备纳 米金属颗粒方面取得了显著的成果, 目前已成功的利用微通道反应器连续合成了多种纳米 金属颗粒, 包括 Au (Nano Lett. 2005, 5, 685)、 Ag (Nano Lett. 2004,4,2227)、 Pt (J. Nanosci.
Nanotechnol. 2004, 4, 788)、 Cu(J. Phys. Chem. B. 2005, 109, 9330)和 Co (Chem. Mater. 2006, 18, 2817) 等, 但利用微通道制备纳米镍的报道并不多见, 主要原因可能是纳米金属颗粒 在合成过程中会在通道内发生沉积而堵塞微通道, 使得反应无法顺利进行。 我们曾利用液 液两相嵌段流的流动形式成功解决了纳米颗粒在微通道内的堵塞问题,但该方法需要在反 应后进行两相分离, 会增加后续处理步骤。 因此, 开发一种既可以连续合成纳米镍颗粒, 同时又操作简便的制备方法显得十分必要。 发明内容 The liquid nickel chemical powder prepared by the above liquid phase chemical reduction method is synthesized in a batch manner, and the dispersing agent is added in the preparation process to prevent the agglomeration of the nano nickel, which brings inconvenience to the subsequent treatment. Patent CN03113326.6 discloses a process and a special equipment for continuously preparing ultrafine nano powder by a precipitation method, which first mixes a nickel salt and a reducing agent in a tank reactor, and then mixes the materials. The reaction is carried out in a tubular reactor equipped with a static mixer, and finally a nano-nickel powder having a good dispersibility and a narrow particle size distribution can be obtained. The whole process is continuous and simple to operate, but conventional reactors have different degrees of "magnification effect" during the amplification process. In recent years, microchannel reactors have achieved remarkable results in the continuous preparation of nano metal particles due to their excellent properties in heat transfer, mass transfer, size control and absence of "amplification effect". Microchannels have been successfully utilized. The reactor continuously synthesizes a variety of nano metal particles, including Au (Nano Lett. 2005, 5, 685), Ag (Nano Lett. 2004, 4, 2227), Pt (J. Nanosci. Nanotechnol. 2004, 4, 788), Cu (J. Phys. Chem. B. 2005, 109, 9330) and Co (Chem. Mater. 2006, 18, 2817), etc., but using microchannels to prepare nano-nickel and Rarely, the main reason may be that nano metal particles will deposit in the channel during the synthesis process and block the microchannel, making the reaction impossible. We have successfully solved the problem of clogging of nanoparticles in microchannels by using the flow pattern of liquid-liquid two-phase block flow. However, this method requires two-phase separation after the reaction, which will increase the subsequent processing steps. Therefore, it is necessary to develop a preparation method that can continuously synthesize nano-nickel particles while being easy to operate. Summary of the invention
本发明的目的是为了克服间歇生产效率较低的缺点,并利用溶剂部分汽化所形成的气 液两相嵌段流的流动形式来解决颗粒在合成过程中微通道的堵塞问题,而提供了一种利用 微通道反应器制备纳米镍粉的方法。 The object of the present invention is to overcome the disadvantages of low batch production efficiency, and to utilize the flow form of the gas-liquid two-phase block flow formed by partial vaporization of the solvent to solve the problem of clogging of the microchannel during the synthesis of the particles, and to provide a A method for preparing nano-nickel powder using a microchannel reactor.
本发明的技术方案为: 一种利用微通道反应器制备纳米镍粉的方法, 具体步骤为: The technical scheme of the invention is: A method for preparing nano nickel powder by using a microchannel reactor, the specific steps are:
1) 分别配制可溶性镍盐的醇溶液 A和含碱的水合肼醇溶液 B; 1) separately preparing a soluble nickel salt alcohol solution A and a base containing hydrated sterol solution B;
2) A液与 B液按照水合肼 /镍离子的摩尔比例 2~10:1分别通过泵注入加热的微混合器 内混合, 混合后的料液直接注入加热的微通道反应器中反应, 收集出料产物; 2) The liquid A and the liquid B are mixed according to the molar ratio of hydrazine hydrate/nickel ion 2~10:1 by pump into the heated micro-mixer, and the mixed liquid is directly injected into the heated microchannel reactor to collect and collect. Discharge product;
3) 产物经离心分离, 洗涤至 pH=6~7后, 隔绝空气保存; 得到纳米镍粉。 3) The product is separated by centrifugation, washed to pH=6~7, and stored in isolation air; nano-nickel powder is obtained.
优选可溶性镍盐为氯化镍、 硫酸镍、 硝酸镍、 乙酸镍, 更优选为氯化镍、 乙酸镍; 可 溶性镍盐的醇溶液的浓度为 0.05~1.0 mol/L。步骤 1)B液中含碱的水合肼溶液的浓度为 0.15-2 mol/L, 其中碱 /水合肼的摩尔比例 0.8~1.2:1。 Preferably, the soluble nickel salt is nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, more preferably nickel chloride or nickel acetate; and the concentration of the alcohol solution of the soluble nickel salt is 0.05 to 1.0 mol/L. Step 1) The concentration of the alkali-containing hydrazine hydrate solution in the B solution is 0.15-2 mol/L, and the molar ratio of the alkali/hydrated hydrazine is 0.8 to 1.2:1.
优选步骤 1)中含碱的水合肼溶液中的碱为 NaOH或 KOH; 优选步骤 1)中溶液 A和溶 液 B中的醇为甲醇、 乙醇、 异丙醇或乙二醇, 更优选为甲醇、 乙醇。 Preferably, the base in the alkali-containing hydrazine hydrate solution in the step 1) is NaOH or KOH; preferably the alcohol in the solution A and the solution B in the step 1) is methanol, ethanol, isopropanol or ethylene glycol, more preferably methanol, Ethanol.
上述步骤 2)中微混合器和微通道反应器的加热温度为 50~90 V。 优选微混合器的通 道直径为 25~200 μ m,物料在微混合器中的停留 10~100ms;微通道反应器的内径为 0.5~3 mm, 物料在微通道反应器内的停留时间为 2~30 min。 The above steps 2) the micro-mixer and the micro-channel reactor are heated at a temperature of 50 to 90 V. Preferably, the micromixer has a channel diameter of 25 to 200 μm, the material stays in the micromixer for 10 to 100 ms, the microchannel reactor has an inner diameter of 0.5 to 3 mm, and the residence time of the material in the microchannel reactor is 2 ~30 min.
本发明的反应装置流程图见图 1。 The flow chart of the reaction apparatus of the present invention is shown in Fig. 1.
有益效果 Beneficial effect
1. 本发明采用微通道反应器进行纳米镍合成, 可实现反应过程的连续可控, 并且操 作简单易行, 不存在"放大效应", 生产过程可实现工业化; 1. The invention adopts a microchannel reactor for nano nickel synthesis, which can realize continuous and controllable reaction process, and is simple and easy to operate, has no "amplification effect", and the production process can be industrialized;
2. 本发明在合成过程中不添加任何其他分散剂或引发剂, 原料成本低廉, 合成的纳 米镍颗粒具有粒径分布窄、 分散性好等优点; 2. The invention does not add any other dispersing agent or initiator in the synthesis process, and the raw material cost is low, and the synthesized nano nickel particles have the advantages of narrow particle size distribution and good dispersibility;
3. 本发明采用溶剂部分汽化形成气液两相嵌段流的流型,可以避免纳米颗粒在微通
道内的堵塞现象, 并且便于产物的后续分离处理。 附图说明 3. The invention adopts a partial vaporization of a solvent to form a gas-liquid two-phase block flow, which can avoid the nano-particles in the micro-pass Blockage in the channel and facilitate subsequent separation of the product. DRAWINGS
图 1为微通道反应器制备纳米镍粉装置流程示意图, 其中 a: 镍盐醇溶液; b: 含碱 的水合肼醇溶液; 1-1和 1-2: 输料泵; 2: 微混合器; 3 : 水浴加热恒温区; 4: 微通道反 应器; 5 : 产物收集罐; 1 is a schematic flow chart of a device for preparing a nano-nickel powder in a microchannel reactor, wherein a: a nickel salt alcohol solution; b: a hydration sterol solution containing a base; 1-1 and 1-2: a feed pump; 2: a micromixer 3: water bath heating constant temperature zone; 4: microchannel reactor; 5: product collection tank;
图 2为实施例 1样品的 X射线衍射图 (XRD ) ; 2 is an X-ray diffraction pattern (XRD) of the sample of Example 1;
图 3为实施例 1样品的透射电子显微镜图 (TEM) ; Figure 3 is a transmission electron micrograph (TEM) of the sample of Example 1;
图 4为实施例 2样品的场发射扫描电子显微镜图 (FESEM)。 具体实施方式 Figure 4 is a field emission scanning electron micrograph (FESEM) of the sample of Example 2. detailed description
实施例 1 Example 1
将 4.75 g氯化镍溶解在 50 ml乙醇中配置 A液, 将 4.71 g水合肼和 3.2 g氢氧化钠加 入 50 ml乙醇中配置 B液, A液和 B液通过泵注入温度为 70 °C通道直径为 100 μ m的微 混合器 (购自德国 IMM公司) 中混合, 停留 60 ms后料液直接注入反应温度为 70 V , 内径为 2 mm的微通道反应器 (购自南京晚晴实业公司) 中停留 3.5 min进行反应, 收集 产物, 产物分别经离心分离, 洗涤至 pH=7后, 隔绝空气保存。 经 XRD表征显示产物为 镍金属, 获得的纳米镍平均粒径为 73 nm, 该样品的样品的 X射线衍射图 (XRD )如图 2 所示, TEM图见图 3所示。 实施例 2 Dissolve 4.75 g of nickel chloride in 50 ml of ethanol and configure liquid A. Add 4.71 g of hydrazine hydrate and 3.2 g of sodium hydroxide to 50 ml of ethanol to configure liquid B. The liquids of liquid A and liquid B are pumped through the pump at a temperature of 70 ° C. The micro-mixer with a diameter of 100 μm (purchased from IMM, Germany) was mixed. After 60 ms, the solution was directly injected into a microchannel reactor with a reaction temperature of 70 V and an inner diameter of 2 mm (purchased from Nanjing Qingqing Industrial Co., Ltd.). The reaction was carried out for 3.5 min, and the product was collected. The product was separated by centrifugation, washed to pH=7, and stored in an isolated atmosphere. XRD showed that the product was nickel metal, and the average nano-nickel particle size was 73 nm. The X-ray diffraction pattern (XRD) of the sample was shown in Figure 2, and the TEM image is shown in Figure 3. Example 2
将 9.51 g氯化镍溶解于 100 ml乙醇中配置 A液, 将 8.83 g水合肼和 6 g氢氧化钠加 入到 100 ml乙醇中配置 B液, A液和 B液通过泵注入温度为 70 °C通道直径为 100 μ m 的微混合器(购自德国 IMM公司)中混合,停留 80 ms后料液直接注入反应温度为 70 °C, 内径为 2 mm的微通道反应器 (购自南京晚晴实业公司) 中停留 5 min进行反应, 收集产 物, 产物分别经离心分离, 洗涤至 pH=6.5后, 将得到的样品隔绝空气保存。 经 XRD表 征显示该样品为镍金属, 获得的纳米镍平均粒径为 65 nm, 该样品的 FESEM图见图 4所 示。 实施例 3 Dissolve 9.51 g of nickel chloride in 100 ml of ethanol to configure liquid A. Add 8.83 g of hydrazine hydrate and 6 g of sodium hydroxide to 100 ml of ethanol to configure liquid B. The liquids of liquid A and liquid B are pumped at a temperature of 70 °C. A micro-mixer with a channel diameter of 100 μm (purchased from IMM, Germany) was mixed. After 80 ms, the solution was directly injected into a microchannel reactor with a reaction temperature of 70 ° C and an inner diameter of 2 mm (purchased from Nanjing Qingqing). In the industrial company, the reaction was carried out for 5 min, and the product was collected. The product was separately centrifuged, washed to pH=6.5, and the obtained sample was stored in air. The XRD shows that the sample is nickel metal, and the obtained nano nickel has an average particle diameter of 65 nm. The FESEM image of the sample is shown in Fig. 4. Example 3
将 2.08 g氯化镍溶解于 50 ml乙醇中配置 A液, 将 4.12 g水合肼和 2.8 g氢氧化钠加
入到 50 ml乙醇中配置 B液, A液和 B液通过泵注入温度为 68 °C通道直径为 50 μ m的 微混合器(购自德国 IMM公司)中混合,停留 50 ms后的料液直接注入反应温度为 68 °C, 内径为 2 mm的微通道反应器 (购自南京晚晴实业公司) 中停留 4 min进行反应, 收集产 物, 产物分别经离心分离, 洗涤至 pH=6.5后, 将得到的样品隔绝空气保存。 经 XRD表 征显样品为镍金属, 获得的纳米镍平均粒径为 45 nm。 实施例 4 Dissolve 2.08 g of nickel chloride in 50 ml of ethanol to configure solution A, and add 4.12 g of hydrazine hydrate and 2.8 g of sodium hydroxide. The liquid B was placed in 50 ml of ethanol, and the liquids A and B were mixed by a pump into a micro-mixer (purchased from IMM, Germany) with a channel diameter of 50 μm, and the solution was kept for 50 ms. The reaction was carried out by directly injecting a microchannel reactor (purchased from Nanjing Nianqing Industrial Co., Ltd.) with a reaction temperature of 68 ° C and an internal diameter of 2 mm for 4 min to collect the product. The product was separately centrifuged and washed to pH=6.5. The resulting sample was stored in air. The sample was characterized by XRD as nickel metal, and the obtained nano-nickel had an average particle diameter of 45 nm. Example 4
将 5.67 g乙酸镍溶解于 60 ml乙醇中配置 A液, 将 8.06 g水合肼和 6.02 g氢氧化钠 加入到 60 ml乙醇中配置 B液, A液和 B液通过泵注入温度为 72 °C通道直径为 50 μ m 的微混合器(购自德国 IMM公司)中混合,停留 75 ms后料液直接注入反应温度为 72 。C, 内径为 l mm的微通道反应器 (购自南京晚晴实业公司) 中停留 8 min进行反应, 收集出 料产物, 产物分别经离心分离, 洗涤至 pH=6.5后, 将得到的样品隔绝空气保存, 经 XRD 表征显示该样品为镍金属。 获得的纳米镍平均粒径为 50 nm。 实施例 5 Dissolve 5.67 g of nickel acetate in 60 ml of ethanol to configure liquid A. Add 8.06 g of hydrazine hydrate and 6.02 g of sodium hydroxide to 60 ml of ethanol to configure liquid B. The liquids of liquid A and liquid B are pumped through a pump at a temperature of 72 ° C. The micromixer with a diameter of 50 μm (purchased from IMM, Germany) was mixed and the solution was directly injected into the reaction temperature for 72 ms. C, a microchannel reactor with an inner diameter of l mm (purchased from Nanjing Qingqing Industrial Co., Ltd.) was allowed to react for 8 min, and the product was collected. The product was separated by centrifugation and washed to pH=6.5 to isolate the sample. It was stored in air and characterized by XRD to show that the sample was nickel metal. The obtained nano nickel has an average particle diameter of 50 nm. Example 5
将 8.32 g氯化镍溶解于 100 ml甲醇中配置 A液,将 9.28 g水合肼和 5.67 g氢氧化钠加入到 100 m甲醇中配置 B液, A液和 B液通过泵注入温度为 62 °C通道直径为 25 μ m的微混合器 Dissolve 8.32 g of nickel chloride in 100 ml of methanol to configure liquid A, add 9.28 g of hydrazine hydrate and 5.67 g of sodium hydroxide to 100 m of methanol to configure liquid B. The liquids of liquid A and liquid B are pumped at a temperature of 62 °C. Micro-mixer with a channel diameter of 25 μm
(购自德国 IMM公司)中混合, 40 ms后料液直接注入反应温度为 62 °C, 内径为 1 mm的微 通道反应器 (购自南京晚晴实业公司) 中停留 7 min进行反应, 收集出料产物, 产物分别 经离心分离, 洗涤至 pH=6.5后, 将得到的样品隔绝空气保存。经 XRD表征显示该样品为镍 金属, 获得的纳米镍平均粒径为 55 nm。
(purchased from IMM, Germany), after 40 ms, the feed was directly injected into the microchannel reactor (purchased from Nanjing Nianqing Industrial Co., Ltd.) with a reaction temperature of 62 °C and an internal diameter of 1 mm for 7 min to carry out the reaction. The product was discharged, and the product was separately centrifuged, washed to pH = 6.5, and the obtained sample was stored in air. XRD analysis showed that the sample was nickel metal, and the average nano-nickel particle size was 55 nm.
Claims
1. 一种利用微通道反应器制备纳米镍粉的方法, 其具体步骤为: A method for preparing nano nickel powder by using a microchannel reactor, the specific steps of which are:
1) 分别配制可溶性镍盐的醇溶液 A和含碱的水合肼醇溶液 B; 1) separately preparing a soluble nickel salt alcohol solution A and a base containing hydrated sterol solution B;
2) A液与 B液按照水合肼 /镍离子的摩尔比例 2~10:1分别通过泵注入加热的微混合器 内混合, 混合后的料液直接注入加热的微通道反应器中反应, 收集出料产物; 2) The liquid A and the liquid B are mixed according to the molar ratio of hydrazine hydrate/nickel ion 2~10:1 by pump into the heated micro-mixer, and the mixed liquid is directly injected into the heated microchannel reactor to collect and collect. Discharge product;
3) 产物经离心分离, 洗涤至 pH=6~7后, 隔绝空气保存; 得到纳米镍粉。 3) The product is separated by centrifugation, washed to pH=6~7, and stored in isolation air; nano-nickel powder is obtained.
2. 按照权利要求 1所述的方法, 其特征在于步骤 1)中可溶性镍盐为氯化镍、 硫酸镍、 硝 酸镍、 乙酸镍; 其浓度为 0.05~1.0 mol/L。 2. The method according to claim 1, wherein the soluble nickel salt in the step 1) is nickel chloride, nickel sulfate, nickel nitrate, nickel acetate; and the concentration thereof is 0.05 to 1.0 mol/L.
3. 按照权利要求 1 所述的方法, 其特征在于步骤 1)中含碱的水合肼醇溶液的浓度为 0.15-2 mol/L, 其中碱 /水合肼的摩尔比例 0.8~1.2:1。 3. A method according to claim 1, characterized in that the concentration of the alkali-containing hydrazine hydrate solution in step 1) is 0.15-2 mol/L, wherein the molar ratio of alkali/hydrated hydrazine is 0.8 to 1.2:1.
4. 按照权利要求 1所述的方法,其特征在于步骤 1)中含碱的水合肼醇溶液中的碱为 NaOH 或 KOHo 4. The method according to claim 1, wherein the base in the alkali-containing hydration sterol solution in step 1) is NaOH or KOHo
5. 按照权利要求 1所述的方法,其特征在于步骤 1)中溶液 A和溶液 B中的醇为甲醇、乙 醇、 异丙醇或乙二醇。 5. Process according to claim 1, characterized in that the alcohol in solution A and solution B in step 1) is methanol, ethanol, isopropanol or ethylene glycol.
6. 按照权利要求 1所述的方法, 其特征在于步骤 2)中微混合器和微通道反应器的加热温 度为 50~90 V。 6. The method of claim 1 wherein the step 2) the micromixer and the microchannel reactor are heated to a temperature of 50 to 90 volts.
7. 按照权利要求 1所述的方法, 其特征在于步骤 2)中微混合器的通道直径为 25~200 μ m, 物料在微混合器中的停留 10~100ms; 微通道反应器的内径为 0.5~3 mm, 物料在 微通道反应器内的停留时间为 2~30 min。 7. The method according to claim 1, wherein the micro-mixer has a channel diameter of 25 to 200 μm and the material stays in the micro-mixer for 10 to 100 ms; the inner diameter of the microchannel reactor is 0.5~3 mm, the residence time of the material in the microchannel reactor is 2~30 min.
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