CN113500204A - Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt - Google Patents
Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt Download PDFInfo
- Publication number
- CN113500204A CN113500204A CN202110772077.0A CN202110772077A CN113500204A CN 113500204 A CN113500204 A CN 113500204A CN 202110772077 A CN202110772077 A CN 202110772077A CN 113500204 A CN113500204 A CN 113500204A
- Authority
- CN
- China
- Prior art keywords
- calcium
- niobium
- molten salt
- chloride
- calcium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt, which comprises the steps of introducing niobium pentachloride gas into calcium chloride molten salt dissolved with metal calcium by using argon, leaching a reaction product by using dilute hydrochloric acid after the reaction is finished, washing the reaction product by using deionized water and absolute ethyl alcohol, and finally drying the reaction product in vacuum to obtain the fine niobium powder. The niobium powder prepared by the method has high purity, small particle size and good sphericity, and the preparation process can be continuously carried out and can be popularized to the preparation of other fine metal powder.
Description
Technical Field
The invention relates to the technical field of preparation of functional metal powder materials, in particular to a method for preparing fine niobium powder by thermally reducing niobium chloride with calcium in calcium chloride molten salt.
Background
The tantalum anode of a high performance capacitor is made of high purity fine tantalum (Ta) powder. However, tantalum is expensive due to limited earth crust resources. Niobium (Nb) has similar physicochemical properties to tantalum, is abundant in reserves, and is 1/20 the price of tantalum. Therefore, the development of niobium capacitors is of great significance. Since the capacitance is proportional to the anode surface area, it has been reported that the anode specific surface area is greater than 5.0 m2The high capacitance of Ta capacitors per g (corresponding to an average anode particle size of less than 70 nm) exceeds 0.2 FV/g. Therefore, it is combinedThe formation of fine, uniform and high purity Nb powders, particularly nano-niobium powders with diameters less than 100nm, is critical to the design of new capacitors with high capacity efficiency.
The existing methods for preparing Nb powder mainly comprise a metallothermic reduction method and an electrochemical reduction method. The metallothermic reduction method comprises an aluminothermic method, a carbothermic method, a sodalothermic method, a magnesiothermic method and a calthermic reduction method, the reduction reaction can strongly release heat in the reaction process to cause the growth of Nb powder grains and powder, and the Nb powder grains and the powder are aggregated and sintered into large particles, so that the Nb nano powder with the grain diameter less than 100nm is difficult to prepare. The electrochemical reduction method comprises an EMR method (electrochemical mediated fused salt calcium thermal reduction reaction), an OS method (calcium thermal reduction and electrolysis combined reaction) and an FFC method (electrolytic metal oxide cathode reaction), and the prepared Nb powder has large particle size and uneven particle size distribution, low current efficiency and high energy consumption.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt, wherein the fine niobium powder is directly obtained from gaseous niobium chloride as a raw material through calcium thermal reduction.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for preparing fine niobium powder by thermally reducing niobium chloride with calcium in calcium chloride molten salt comprises the following steps:
s1, carrying out vacuum pumping dehydration treatment on anhydrous calcium chloride in an atmosphere furnace, then adding metal calcium, heating the atmosphere furnace to a specified reaction temperature, and stirring with argon to promote the metal calcium to be dissolved in calcium chloride molten salt;
s2, introducing the evaporated niobium pentachloride gas into calcium chloride molten salt for dissolving metal calcium by using argon gas, and carrying out calcium thermal reaction to obtain a reduction product;
and S3, leaching the reduction product, washing and drying in vacuum to obtain fine niobium powder.
Further, in step S1, the temperature of the anhydrous calcium chloride is 500 ℃ and the dehydration time is 12 hours.
Further, in step S1, when the mass ratio of the metal calcium to the anhydrous calcium chloride is 1:50, and the reaction temperature specified in the atmosphere furnace is 900-.
Further, in step S2, the flow rate of argon is 10L/min, the evaporation temperature of niobium pentachloride is 170-220 ℃, and the evaporation speed of niobium pentachloride is 0.05-0.16 g/min.
Further, in step S2, metal calcium is continuously added at a speed of 0.135-0.432g/min, and the metal calcium is stirred with argon gas to accelerate the dissolution of the metal calcium in the calcium chloride molten salt.
Further, in step S3, the reduction product is leached with dilute hydrochloric acid.
Furthermore, the concentration ratio of the dilute hydrochloric acid is that the volume ratio of the hydrochloric acid to water is 1: 10.
Further, the solid-to-liquid ratio of the reduction product to dilute hydrochloric acid is more than 0.025g/ml, and the leaching time is 8-12 h.
Further, the reduction product is a mixture of solidified calcium chloride molten salt and niobium product powder.
Compared with the prior art, the invention has the following beneficial effects: the method takes gaseous niobium pentachloride as a raw material, and carries out calcium thermal reduction in calcium chloride molten salt to prepare high-purity niobium powder with the particle size of less than 100nm, and the prepared niobium powder has small particle size and uniform particle size distribution.
In order to make the aforementioned and other objects, features and advantages of the invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
Fig. 1 is an SEM image of the fine niobium powder prepared in the first example of the present invention.
Fig. 2 is an EDS profile of a fine niobium powder prepared in accordance with example one of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
Example one
A method for preparing fine niobium powder by thermally reducing niobium chloride with calcium in calcium chloride molten salt comprises the following steps:
s1, carrying out vacuum-pumping dehydration treatment on anhydrous calcium chloride in an atmosphere furnace, wherein the vacuum-pumping dehydration temperature is 500 ℃, and the dehydration time is 12 hours; then adding metal calcium, wherein the mass ratio of the added metal calcium to the anhydrous calcium chloride is 1:50, heating the atmosphere furnace to the specified reaction temperature of 900 ℃, stirring with argon to promote the metal calcium to be dissolved in the calcium chloride molten salt, and simultaneously, before the metal calcium reacts, keeping the metal calcium in the calcium chloride molten salt in a saturated state;
s2, introducing the evaporated niobium pentachloride gas into calcium chloride molten salt for dissolving metal calcium by using argon gas, and carrying out calcium thermal reaction to obtain a reduction product; the flow rate of argon is 10L/min; the evaporation temperature of the niobium pentachloride is 170 ℃, and the evaporation speed of the niobium pentachloride is 0.05 g/min; the reduction product is a mixture of solidified calcium chloride molten salt and niobium product powder;
and S3, leaching the reduction product by using dilute hydrochloric acid, washing and drying in vacuum to obtain fine niobium powder.
In this embodiment, in step S2, the metal calcium is continuously added at a speed of 0.135g/min, and the metal calcium is stirred with argon gas to accelerate the dissolution of the metal calcium in the calcium chloride molten salt.
In this embodiment, in step S3, the concentration ratio of the dilute hydrochloric acid is 1:10 by volume of hydrochloric acid to water.
In the embodiment, the solid-to-liquid ratio of the reduction product to the dilute hydrochloric acid is more than 0.025g/ml, and the leaching time is 8 hours.
The SEM image of the fine niobium powder obtained is shown in fig. 1, and the EDS profile thereof is shown in fig. 2.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for preparing fine niobium powder by thermally reducing niobium chloride with calcium in calcium chloride molten salt is characterized by comprising the following steps:
s1, carrying out vacuum pumping dehydration treatment on anhydrous calcium chloride in an atmosphere furnace, then adding metal calcium, heating the atmosphere furnace to a specified reaction temperature, and stirring with argon to promote the metal calcium to be dissolved in calcium chloride molten salt;
s2, introducing the evaporated niobium pentachloride gas into calcium chloride molten salt for dissolving metal calcium by using argon gas, and carrying out calcium thermal reaction to obtain a reduction product;
and S3, leaching the reduction product, washing and drying in vacuum to obtain fine niobium powder.
2. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 1, characterized in that: in step S1, the vacuum-pumping dehydration temperature of the anhydrous calcium chloride is 500 ℃, and the dehydration time is 12 h.
3. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 1, characterized in that: in step S1, the mass ratio of the metal calcium to the anhydrous calcium chloride is 1:50, and when the reaction temperature specified in the atmosphere furnace is 900-1000 ℃, the metal calcium in the calcium chloride molten salt is in a saturated state before the metal calcium reacts.
4. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 1, characterized in that: in step S2, the flow rate of argon is 10L/min, the evaporation temperature of niobium pentachloride is 170-220 ℃, and the evaporation speed of niobium pentachloride is 0.05-0.16 g/min.
5. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 1, characterized in that: and step S2, continuously adding the metal calcium at the speed of 0.135-0.432g/min, stirring with argon gas, and accelerating the dissolution of the metal calcium in the calcium chloride molten salt.
6. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 1, characterized in that: in step S3, the reduction product is leached with dilute hydrochloric acid.
7. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 6, characterized in that: the concentration ratio of the dilute hydrochloric acid is that the volume ratio of the hydrochloric acid to water is 1: 10.
8. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 6, characterized in that: the solid-liquid ratio of the reduction product to the dilute hydrochloric acid is more than 0.025g/ml, and the leaching time is 8-12 h.
9. The method for preparing fine niobium powder by calcium thermal reduction of niobium chloride in calcium chloride molten salt according to claim 1, characterized in that: the reduction product is a mixture of solidified calcium chloride molten salt and niobium product powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772077.0A CN113500204A (en) | 2021-07-08 | 2021-07-08 | Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772077.0A CN113500204A (en) | 2021-07-08 | 2021-07-08 | Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113500204A true CN113500204A (en) | 2021-10-15 |
Family
ID=78011650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110772077.0A Pending CN113500204A (en) | 2021-07-08 | 2021-07-08 | Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113500204A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2252413A1 (en) * | 1973-11-22 | 1975-06-20 | Ishizuka Hiroshi | Reducing appts. for difficulty reducible metal chlorides - comprises two heated chambers joined by a duct with attached gas flowmeter |
| US4725312A (en) * | 1986-02-28 | 1988-02-16 | Rhone-Poulenc Chimie | Production of metals by metallothermia |
| CN1382548A (en) * | 2002-03-30 | 2002-12-04 | 宁夏东方钽业股份有限公司 | Method for producing niobium and/or tantalum powder |
| CN1410209A (en) * | 2001-09-29 | 2003-04-16 | 宁夏东方钽业股份有限公司 | Preparation method of high specific surface area tantalum powder and/or niobium powder |
| CN1449879A (en) * | 2003-04-30 | 2003-10-22 | 北京科技大学 | Method for processing microtantalum and/or niobium powder and powder made by said method |
| WO2004007808A1 (en) * | 2002-07-16 | 2004-01-22 | Cabot Supermetals K.K. | Method and apparatus for producing niobium powder or tantalum powder |
| CN1607055A (en) * | 1998-05-06 | 2005-04-20 | H.C.施塔克公司 | Metal powders prepared by reduction of related oxides with gaseous magnesium |
| CN1694973A (en) * | 2002-11-04 | 2005-11-09 | 巴西冶金采矿公司 | A process for the production of niobium and/or tantalum powder with large surface area |
-
2021
- 2021-07-08 CN CN202110772077.0A patent/CN113500204A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2252413A1 (en) * | 1973-11-22 | 1975-06-20 | Ishizuka Hiroshi | Reducing appts. for difficulty reducible metal chlorides - comprises two heated chambers joined by a duct with attached gas flowmeter |
| US4725312A (en) * | 1986-02-28 | 1988-02-16 | Rhone-Poulenc Chimie | Production of metals by metallothermia |
| CN1607055A (en) * | 1998-05-06 | 2005-04-20 | H.C.施塔克公司 | Metal powders prepared by reduction of related oxides with gaseous magnesium |
| CN1410209A (en) * | 2001-09-29 | 2003-04-16 | 宁夏东方钽业股份有限公司 | Preparation method of high specific surface area tantalum powder and/or niobium powder |
| CN1382548A (en) * | 2002-03-30 | 2002-12-04 | 宁夏东方钽业股份有限公司 | Method for producing niobium and/or tantalum powder |
| WO2004007808A1 (en) * | 2002-07-16 | 2004-01-22 | Cabot Supermetals K.K. | Method and apparatus for producing niobium powder or tantalum powder |
| CN1694973A (en) * | 2002-11-04 | 2005-11-09 | 巴西冶金采矿公司 | A process for the production of niobium and/or tantalum powder with large surface area |
| CN1449879A (en) * | 2003-04-30 | 2003-10-22 | 北京科技大学 | Method for processing microtantalum and/or niobium powder and powder made by said method |
Non-Patent Citations (2)
| Title |
|---|
| 吴全兴: "电容器用铌粉和钽粉制备技术的进展", 《稀有金属快报》 * |
| 王娜等: "熔盐钠热还原NbCl_5制备金属铌粉", 《有色金属(冶炼部分)》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1297364C (en) | Precipitation reduction method of preparing nano-cobalt powder | |
| JP4187953B2 (en) | Method for producing nitrogen-containing metal powder | |
| US6563695B1 (en) | Powdered tantalum, niobium, production process thereof, and porous sintered body and solid electrolytic capacitor using the powdered tantalum or niobium | |
| CN105399100A (en) | Preparation method for nanoporous silicon | |
| EP2368843A1 (en) | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced thereby | |
| CN112662881A (en) | Method for preparing industrial cobalt powder by microwave reduction pyrolysis of cobalt acid lithium battery | |
| CN113106496A (en) | Method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt | |
| Shi et al. | Green synthesis of high-performance porous carbon coated silicon composite anode for lithium storage based on recycled silicon kerf waste | |
| KR101102872B1 (en) | Fabrication Method of Tantalum Powders by Self-propagating High-temperature Synthesis | |
| CN113500204A (en) | Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt | |
| CN111994953A (en) | Sea urchin-shaped niobium pentoxide material and preparation method and application thereof | |
| CN103752841B (en) | A kind of preparation method of copper nanoparticle | |
| CN116710400A (en) | Electrode material for extracting lithium from salt lake by electrochemical deintercalation method, preparation method and application thereof | |
| CN114105145B (en) | Carbon-coated three-dimensional porous silicon anode material and preparation method and application thereof | |
| JPH11322335A (en) | Gallium oxide and its production | |
| CN108987707A (en) | A kind of lithium ion battery phosphor-copper negative electrode material and preparation method thereof | |
| CN115188928A (en) | Preparation method of nitrogen-doped MXene sulfur positive electrode | |
| CN110739454B (en) | Negative electrode material and preparation method thereof | |
| CN115305521A (en) | Method for preparing metal niobium by molten salt electrolysis | |
| CN110947979B (en) | Method for synthesizing superfine single crystal nickel powder by solvothermal method | |
| CN114989008B (en) | Ferrous oxalate with tubular microstructure, preparation method and application thereof | |
| JP2001172701A (en) | Niobium powder, producing method therefor, porous sintered body using same niobium powder and solid electrolytic capacitor | |
| CN113215591B (en) | Molten salt electrochemical method for preparing silicon dioxide nanotubes and silicon nanotubes without additional addition of inducer | |
| JP2008095200A (en) | Nitrogen-containing metal powder, its manufacturing method, and porous sintered compact and solid electrolytic capacitor using the metal powder | |
| CN115704099A (en) | Method for preparing metal titanium and nano carbon material by molten salt electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211015 |
|
| RJ01 | Rejection of invention patent application after publication |