CN100439014C - Preparation method and equipment for nano-grade superfine cobalt powder - Google Patents
Preparation method and equipment for nano-grade superfine cobalt powder Download PDFInfo
- Publication number
- CN100439014C CN100439014C CNB2006100312009A CN200610031200A CN100439014C CN 100439014 C CN100439014 C CN 100439014C CN B2006100312009 A CNB2006100312009 A CN B2006100312009A CN 200610031200 A CN200610031200 A CN 200610031200A CN 100439014 C CN100439014 C CN 100439014C
- Authority
- CN
- China
- Prior art keywords
- powder
- preparation
- cobalt
- nano
- thermal reduction
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention discloses a preparation method and a device of nanometer ultrafine cobalt powder. The preparation method comprises the following steps: (1), the concentration of a raw material CoCl2 solution for preparing ultrafine cobalt carbonate powder is from 70 to 120 g/l, the concentration of an NH4. HCO3 solution is a saturated concentration, and reaction temperature is from 25 to 50 DEG C. The CoCl2 solution is added in a reactor at a speed of 20 to 100 L/min, the NH4. HCO3 saturated solution is added in the reactor at a speed of 60 to 400 L/min, and ageing time is from 0.5 to 2.0 hours; (2), the ultrafine cobalt carbonate powder is thermally reduced by hydrogen or is thermally decomposed in a high temperature electric furnace at 300 to 500 DEG C. An exhaust pressure stabilizing guide tube provided with a valve and a mechanical boat pusher are arranged at the front end of a feeding port at the middle part of the furnace end of the high temperature electric furnace, a heating mechanism of a furnace body is independently arranged in five to eight sections, and two to three double layer water cooling mechanisms, a stop valve and a tasimeter are arranged at a furnace tail. The present invention has the advantages of short process steps, simple and convenient control of technological conditions, stable preparation processes, high preparation efficiency and low cost, and can continuously prepare the nanometer cobalt powder and high quality ultrafine cobalt oxide powder in batches.
Description
Technical field
The present invention relates to a kind of preparation method and equipment of super-fine cobalt powder, especially relate to a kind of preparation method and equipment of nano-grade superfine cobalt powder.
Background technology
When the cobalt powder particle little to or during near nano-grade size, specific area that it is huge and superior chemical property, be applied in main quality index aspect such as high-power high-energy battery, ultra-fine high strength cemented carbide, catalyst, show a series of excellent physical chemical property.Therefore prepare the nanometre grade cobalt powder material, just become the target that current scientific and technological industry is generally pursued.
The a large amount of cobalt powder materials that use of current industrial, all be that the traditional cobalt oxalate of employing is a presoma, make by traditional high-temperature electric resistance furnace reduction, the subject matter of the powder of gained is that the powder dispersion is inhomogeneous, granule size and pattern are irregular, be difficult to make active good, specific area big, like spherical nano-cobalt powder.
The preparation method that the Chinese invention patent application discloses a kind of nano-grade superfine cobalt powder No. 200410068855.4, this method adopt air-flow ullrasonic spraying transformation approach to make nanoscale CoO earlier
xPresoma is again through burning, shearing, broken, centrifugal, air-dry, then through tube furnace H
2Reduction makes nano-cobalt powder, and this method operation is tediously long, and control is complicated, is difficult to industrialization.Chinese patent 200510011735.5 discloses the method for a kind of precipitation-reduction method for preparing nanometer cobalt powder, is with cobalt saline solution and NaOH or KOH reaction generation colloidal precipitation Co (OH)
2, flush away acid group and Na repeatedly
+Ion makes presoma Co (OH) through vacuum drying
2Powder is used H again in reduction furnace
2Nano-cobalt powder is made in reduction.The precipitating reagent that this method adopted not only costs an arm and a leg, and flush away Na
+The ion operation is tediously long, the process implementing difficulty.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, provide a kind of operation shorter, control easyly, process implementing is easy to the preparation method and the equipment of nano-grade superfine cobalt powder.
The objective of the invention is to be achieved through the following technical solutions, it may further comprise the steps: the presoma of (1) nanoscale cobalt powder---ultra tiny cobalt carbonate (CoCO
3) powder prepares raw materials used solution and be: CoCl
2Solution concentration 82g/l～200g/l, NH
4HCO
3Solution concentration is 20wt%-30wt%, 30 ℃～50 ℃ of reaction synthesis temperatures, and PH=7.2～7.4, material solution adds reactor speed: CoCl
2Solution 20-100L/min, NH
4HCO
3Solution is 60-400L/min; Mixing speed 500-1000r/min, digestion time 0.8-1.8 hour; Preparation facilities can be selected the disclosed preparation facilities of Chinese invention patent application CN1686828A " a kind of preparation facilities of superfine powder of cobalt carbonate and technology " for use; (2) the ultramicro powder of cobalt carbonate thermal reduction can be in the conventional high-temperature electric furnace with hydrogen reduction or thermal decomposition and make, preferred version is that the following ultramicro powder of cobalt carbonate thermal reduction electric furnace of selecting for use the applicant to invent is realized, 300 ℃-500 ℃ of thermal reduction or heat decomposition temperatures (preferred 350 ℃-450 ℃).
Described ultramicro powder of cobalt carbonate thermal reduction electric furnace comprises burner, the body of heater of attemperating unit is housed, be provided with the stove tail of discharging opening and hydrogen inlet and hydrogen flowmeter, boiler tube, burn boat, it is characterized in that, described burner length is 2200mm-3000mm (preferred 2400mm-2600mm), the burner middle part is provided with charging aperture, and the charging aperture front end is established exhaust voltage stabilizing conduit and the mechanical push-in elevator that has valve (preferably ball valve); The appearance and size of described body of heater is: long 4000mm-4600mm (preferred 4100mm-4300mm), wide 1220mm-1420mm, high 1550mm-1750mm, two-tube heating arrangements divide 5-8 section (preferred 6 sections) independent setting; The long 3600-4400mm of described stove tail (preferred 3900mm-4100mm) is provided with double-deck water-cooled mechanism, and water-cooled mechanism divides the 2-3 section independently to be provided with, and stop valve and differential manometer are equipped with in close discharging opening place, and the specified heating-up temperature of described body of heater can be 700 ℃-900 ℃; Described stove tail can be made of stainless steel, and stove tail tail end discharging opening place establishes the good fire door of air-tightness; Described boiler tube should adopt heat-resisting, corrosion resistant stainless steel to make; Described burning boat should divide upper and lower two-layer, adopts high temperature resistant cast steel to make.
The preparation method of the present invention's nano-grade superfine cobalt powder, operation is brief, and process conditions control is easy, and process implementing is very easy to, low cost of manufacture.
Use the present invention's ultramicro powder of cobalt carbonate thermal reduction equipment, but continuous batch makes nanoscale cobalt powder and high-quality ultra tiny cobalt protoxide powder, preparation process is stable, the preparation efficiency height, and preparation cost is low.
Description of drawings
Accompanying drawing is the structural representation of the present invention's ultramicro powder of cobalt carbonate thermal reduction electric furnace one embodiment.
The specific embodiment
Below in conjunction with drawings and Examples, the present invention's the ultramicro powder of cobalt carbonate thermal reduction electric furnace and the preparation method of nano-grade superfine cobalt powder are described further.
Introduce an embodiment of the present invention's ultramicro powder of cobalt carbonate thermal reduction electric furnace at first in conjunction with the accompanying drawings.
With reference to accompanying drawing, the present invention's ultramicro powder of cobalt carbonate thermal reduction electric furnace embodiment comprises burner, body of heater, stove tail, boiler tube, burn boat, attemperating unit, described burner place on the support 11, length is 2500mm, the burner middle part is provided with charging aperture 1, and charging aperture 1 front end vertical direction is provided with the exhaust voltage stabilizing conduit 4 of dribbling valve 3, and horizontal direction is provided with mechanical push-in elevator 2; Described body of heater 6 places on the support 12, its appearance and size is: long 4200mm, wide 1320mm, high 1650mm, two-tube heating arrangements divides 6 sections independent settings, heater element is the Cr20Ni80 material, design heating power 72kw, specified heating-up temperature is 700 ℃-900 ℃, the thermocouple 5 of attemperating unit is loaded on the body of heater 6, attemperating unit is front and back opening door temperature-controlling cabinets (not drawing among the figure), design control power 90kw adopts controllable silicon coupling intelligent digital thermometric instrument and NiCr-NiSi thermocouple, and furnace temperature is carried out 6 sections demonstrations and control automatically, temperature is carried out PID and is regulated, temperature control precision ± 2 ℃; The long 4000mm of described stove tail is provided with double-deck water-cooled mechanism, and water-cooled mechanism divides 2 sections independent settings, makes of stainless steel, is supported by pillar 13, is provided with hydrogen (H near stove tail front end place
2) inlet and hydrogen flowmeter 7, stove tail tail end is provided with the discharging opening 10 that the good fire door of air-tightness is housed, and near the top of discharging opening 10 stop valve 8 and differential manometer 9 is housed; Described boiler tube (not drawing among the figure) adopts heat-resisting, corrosion resistant stainless steel to make; Described burning boat divides upper and lower two-layer, adopts high temperature resistant cast steel to make.
Introduce two nano-grade superfine cobalt powder preparation methods' embodiment below.
Embodiment 1
(1) presoma of nanoscale cobalt powder---ultramicro powder of cobalt carbonate prepares raw materials used solution and is:
CoCl
2Solution contains Co
2+82g/l, NH
4HCO
3Concentration is 25wt%, 30 ℃ of reaction synthesis temperatures, and PH=7.4 adds reactor speed: CoCl
2Solution 30L/min, NH
4HCO
3Solution is 100L/min: mixing speed 600r ' min, digestion time 1.0 hours; Preparation facilities adopts the disclosed isolated plant of CN1686828A, the CoCO of preparation
3Powder, its main chemical compositions: Ee, Cu, Mn, Ni, Pb, Zn, Ca, Mg, Cl
-Deng impurity content respectively≤O.01%, Co≤50%, H
2O≤0.2%, the μ m of particle mean size≤O.1; (2) thermal reduction places the above the present invention's ultramicro powder of cobalt carbonate thermal reduction electric furnace to carry out thermal reduction (1) ultramicro powder of cobalt carbonate that makes of step, specific operation process is as follows: at first globe valve 3 is opened, stop valve 8 is closed, pure hydrogen is imported boiler tube through hydrogen flowmeter 7, furnace air is driven clean thoroughly (1～2 hour), and then each band to stove send electrical heating to be warming up to 360 ℃, and is simultaneously that the cooling water channel of stove tail is open-minded, when each band temperature reaches setting value, with CoCO
3Material is put into the double-deck boat that burns, and will burn boat with mechanical push-in elevator 2 and push boiler tube by charging aperture 1, and regulate hydrogen flowmeter 7 simultaneously, enters the hydrogen reduction process; Waste gas through globe valve 3 by 4 emptyings of exhaust voltage stabilizing conduit; At last, product is gone out by discharging opening 10 hooks, and product is carried out inert gas shielding rapidly, and so charging → push away boat → reaction → cooling → discharging → protection move in circles, but just continuous batch is prepared specific area 〉=30m
2/ g, pattern are sphere or class sphere, and its average grain diameter is 50～100nm, the nanoscale high energy cobalt powder of oxygen content≤0.2%.
Embodiment 2
CoCl
2Solution concentration contains Co
2+150g/l, 45 ℃ of reaction synthesis temperatures, PH=7.2 adds reactor speed: CoCl
2Solution 90L/min, NH
4HCO
3Saturated solution is 300L/min; Mixing speed 8000r/min, digestion time 1.5 hours; 400 ℃ of ultramicro powder of cobalt carbonate thermal reduction temperature, other is with embodiment 1.Can prepare specific area 〉=40m continuously
2/ g sphere or class sphere, particle mean size are 30～50nm, the nanoscale high energy cobalt powder of oxygen content≤0.2%.
Claims (6)
1, a kind of preparation method of nano-grade superfine cobalt powder is characterized in that, may further comprise the steps: the presoma of (1) nanoscale cobalt powder---the ultramicro powder of cobalt carbonate preparation, raw materials used solution concentration is: CoCl
2Solution concentration 82～200g/l, NH
4HCO
3Solution concentration 20wt%-30wt%, 30～50 ℃ of reaction synthesis temperatures, PH=7.2～7.4, material solution adds reactor speed: CoCl
2Solution 20-100L/min, NH
4HCO
3Saturated solution is 60-400L/min; Mixing speed 500-1000r/min, digestion time 0.8-1.8 hour; (2) ultramicro powder of cobalt carbonate thermal reduction, in high-temperature electric resistance furnace is 300 ℃-500 ℃ with hydrogen thermal reduction temperature.
2, the ultramicro powder of cobalt carbonate thermal reduction electric furnace of the preparation method of nano-grade superfine cobalt powder as claimed in claim 1 use, comprise burner, the body of heater of attemperating unit is housed, be provided with the stove tail of discharging opening and hydrogen inlet and hydrogen flowmeter, boiler tube burns boat, it is characterized in that, described burner length is 2200mm-3000mm, and the burner middle part is provided with charging aperture, and the charging aperture front end is established exhaust voltage stabilizing conduit and the mechanical push-in elevator that has valve; The appearance and size of described body of heater is: long 4000mm-4600mm, and wide 1220mm-1420mm, high 1550mm-1750mm, two-tube heating arrangements divide the 5-8 section independently to be provided with; The long 3600-4400mm of described stove tail is provided with double-deck water-cooled mechanism, and water-cooled mechanism divides the 2-3 section independently to be provided with, near stop valve and differential manometer being housed the discharging opening place.
3, the ultramicro powder of cobalt carbonate thermal reduction electric furnace of the preparation method of nano-grade superfine cobalt powder as claimed in claim 2 use is characterized in that the long 4100mm-4300mm of described body of heater.
4, the ultramicro powder of cobalt carbonate thermal reduction electric furnace that uses as the preparation method of claim 2 or 3 described nano-grade superfine cobalt powders is characterized in that the long 3900mm-4100mm of described stove tail.
5, the ultramicro powder of cobalt carbonate thermal reduction electric furnace that uses as the preparation method of claim 2 or 3 described nano-grade superfine cobalt powders is characterized in that, described two-tube heating arrangements divides 6 sections independent settings.
6, the ultramicro powder of cobalt carbonate thermal reduction electric furnace of the preparation method of nano-grade superfine cobalt powder as claimed in claim 4 use is characterized in that, described two-tube heating arrangements divides 6 sections independent settings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100312009A CN100439014C (en) | 2006-01-26 | 2006-01-26 | Preparation method and equipment for nano-grade superfine cobalt powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100312009A CN100439014C (en) | 2006-01-26 | 2006-01-26 | Preparation method and equipment for nano-grade superfine cobalt powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1840266A CN1840266A (en) | 2006-10-04 |
| CN100439014C true CN100439014C (en) | 2008-12-03 |
Family
ID=37029556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100312009A Expired - Fee Related CN100439014C (en) | 2006-01-26 | 2006-01-26 | Preparation method and equipment for nano-grade superfine cobalt powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100439014C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100546740C (en) * | 2007-07-09 | 2009-10-07 | 深圳市格林美高新技术股份有限公司 | A kind of super-fine cobalt powder and manufacturing process thereof |
| CN103028735B (en) * | 2011-09-30 | 2014-10-15 | 深圳市格林美高新技术股份有限公司 | Preparation method of semi-micrometer cobalt powder |
| CN104722778B (en) * | 2013-12-19 | 2017-07-25 | 荆门市格林美新材料有限公司 | A kind of synthetic method of hypoxemia super-fine cobalt powder |
| CN109809374B (en) * | 2019-01-16 | 2022-07-19 | 武汉工程大学 | Push boat type semi-continuous boron nitride nanotube preparation furnace and use method thereof |
| CN113774193B (en) * | 2020-06-09 | 2023-05-16 | 安泰天龙（宝鸡）钨钼科技有限公司 | Boat pushing furnace |
| CN113909485B (en) * | 2021-10-11 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN114905048B (en) * | 2022-06-02 | 2023-06-16 | 兰州理工大学 | Preparation method of nano cobalt powder for additive manufacturing |
| CN115872456A (en) * | 2022-11-18 | 2023-03-31 | 贵州雅友新材料有限公司 | Preparation method and application of nano spherical cobalt carbonate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034689A (en) * | 1987-12-09 | 1989-08-16 | 中国科学院化工冶金研究所 | The preparation method of submicron metal |
| CN1154279A (en) * | 1995-10-27 | 1997-07-16 | H·C·施塔克公司 | Ultrafine cobalt metal powder, process for production thereof and use of cobalt metal powder and of cobalt carbonate |
| US20040211294A1 (en) * | 2002-12-30 | 2004-10-28 | Kim Byung Kee | Method of producing nanophase W powder by low-pressure vapor phase reaction |
| CN1586772A (en) * | 2004-07-09 | 2005-03-02 | 北京科技大学 | Process for preparing nano grade super fine cobalt powder |
| WO2005040038A1 (en) * | 2003-10-23 | 2005-05-06 | Zempachi Ogumi | Method and device for producing fine particles |
| CN1686828A (en) * | 2005-04-15 | 2005-10-26 | 湖南凯丰新材料有限公司 | Production equipment and technique for ultramicro powder of cobalt carbonate |
| CN1686650A (en) * | 2005-05-18 | 2005-10-26 | 北京科技大学 | Precipitation reduction method of preparing nano-cobalt powder |
-
2006
- 2006-01-26 CN CNB2006100312009A patent/CN100439014C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034689A (en) * | 1987-12-09 | 1989-08-16 | 中国科学院化工冶金研究所 | The preparation method of submicron metal |
| CN1154279A (en) * | 1995-10-27 | 1997-07-16 | H·C·施塔克公司 | Ultrafine cobalt metal powder, process for production thereof and use of cobalt metal powder and of cobalt carbonate |
| US20040211294A1 (en) * | 2002-12-30 | 2004-10-28 | Kim Byung Kee | Method of producing nanophase W powder by low-pressure vapor phase reaction |
| WO2005040038A1 (en) * | 2003-10-23 | 2005-05-06 | Zempachi Ogumi | Method and device for producing fine particles |
| CN1586772A (en) * | 2004-07-09 | 2005-03-02 | 北京科技大学 | Process for preparing nano grade super fine cobalt powder |
| CN1686828A (en) * | 2005-04-15 | 2005-10-26 | 湖南凯丰新材料有限公司 | Production equipment and technique for ultramicro powder of cobalt carbonate |
| CN1686650A (en) * | 2005-05-18 | 2005-10-26 | 北京科技大学 | Precipitation reduction method of preparing nano-cobalt powder |
Non-Patent Citations (2)
| Title |
|---|
| 室温固相反应制备纳米Co3O4粉体. 庄稼，迟燕华，王曦，王清成，杨定明，贾殿赠.无机材料学报，第16卷第6期. 2001 |
| 室温固相反应制备纳米Co3O4粉体. 庄稼，迟燕华，王曦，王清成，杨定明，贾殿赠.无机材料学报，第16卷第6期. 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1840266A (en) | 2006-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100439014C (en) | Preparation method and equipment for nano-grade superfine cobalt powder | |
| CN109019701B (en) | Preparation method of rock salt type (MgCoCuNiZn) O high-entropy oxide powder material | |
| US20120237440A1 (en) | Method for producing hydrogen by means of thermochemical water-splitting, and device for producing hydrogen | |
| CN111908519A (en) | High-capacity nickel-rich precursor, positive electrode material and preparation method thereof | |
| CN106044849A (en) | Technology for preparing nano-metallic oxide powder with DC (direct-current) plasma method | |
| CN101138793A (en) | Nanometer powdered iron producing technique | |
| CN104944471A (en) | Tungsten doped bronze powder having high infrared shielding property and synthesis method of doped tungsten bronze powder | |
| CN105720242A (en) | Method for modifying lithium ion battery cathode material | |
| CN105514413A (en) | Lithium ion anode and cathode materials atmosphere immersive sintering process and related sintering device | |
| CN101891193A (en) | Sol-gel Method for preparing nano vanadium carbide | |
| CN102134073B (en) | Preparation method of ultrafine tantalum carbide powder | |
| CN2859420Y (en) | A pyrogenation hydrogen-deoxidizing multifunctional high-temperature electric furnace | |
| CN106082156A (en) | One is prepared Li by ferrophosphorusxfeypzo4method | |
| CN107758669A (en) | A kind of method that propyl alcohol reduction prepares Molybdenum carbide powders | |
| CN109019668B (en) | Method for preparing superfine active zinc oxide powder by hot ball milling oxidation | |
| CN107737943B (en) | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder | |
| CN103146935B (en) | Pyrolyzing furnace for preparing nickel rod through chemical vapor deposition method and method for preparing nickel rod | |
| CN102849784B (en) | Plasma (orifice) gas phase reaction produces the method and apparatus of nano zine oxide | |
| CN101774024A (en) | Preparation method of tungsten-cobalt composite oxide powder | |
| CN104355337A (en) | Preparation method of spherical lithium ion batteries cathode material | |
| CN104300109A (en) | Preparation method of spherical lithium nickel-cobalt-manganese oxide | |
| CN104591280A (en) | Preparation process and device for smelting antimony trioxide by using natural gas | |
| CN115784309B (en) | Flower-like tungsten disulfide micron particles, and preparation method and application thereof | |
| CN107739046A (en) | A kind of preparation method of high whiteness electrical-conductive nanometer Zinc oxide powder | |
| CN103382024A (en) | Pyrolysis preparation method of size-controllable carbon balls |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081203 Termination date: 20100228 |