CN102764895A - Device and method for preparing high-purity ultrafine nickel powder - Google Patents
Device and method for preparing high-purity ultrafine nickel powder Download PDFInfo
- Publication number
- CN102764895A CN102764895A CN2012102689255A CN201210268925A CN102764895A CN 102764895 A CN102764895 A CN 102764895A CN 2012102689255 A CN2012102689255 A CN 2012102689255A CN 201210268925 A CN201210268925 A CN 201210268925A CN 102764895 A CN102764895 A CN 102764895A
- Authority
- CN
- China
- Prior art keywords
- reaction tube
- tube
- nickel powder
- nickel
- gas
- 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.)
- Granted
Links
Images
Abstract
The invention provides a reaction device for preparing ultrafine metal powder and a method for preparing high-purity ultrafine nickel powder. Four small quartz inner tubes are arranged in one large quartz outer tube. A horizontal tube furnace is sleeved outside the outer tube and used for controlling the chemical reaction temperature in the outer tube. A coarse metal powder (or metal oxide) is put in a quartz boat of the third inner tube and chloridized into a metal chloride by high-temperature chlorine or chlorine and carbon monoxide, the latter one volatiles at high temperature and is blown into the fourth inner tube by argon to subject to gas-gas reduction reaction with hydrogen blown into the first inner tube to generate vapor-phase nickel powder, and the vapor-phase nickel powder is mainly taken away from a high-temperature area by the high-speed argon blown into the second inner tube and taken into a low-temperature area and adhered to the low-temperature inner wall of the fourth inner tube, thus the of the grow of the nickel powder through high-temperature sintering can be avoided. When the coarse nickel is chloridized, if no inorganic solid chloride is added, 82% of nickel is chloridized, and if sodium chloride was is added, 97% of nickel is chloridized.
Description
Technical field
The present invention relates to a kind of reaction unit and method for preparing super-fine metal powder, more specifically relate to a kind of apparatus and method that prepare high-purity superfine metal simple substance nickel powder.
Background technology
Usually call superfine powdery material to particle diameter less than the powder body material of 1 μ m.Super-fine metal powder has widely and uses because of its special nature.For example extra-fine nickel powder is a kind of rocket combustion adjuvant, adds it and can make the rocket burn rate improve 100 times.Extra-fine nickel powder is a kind of as submicron particle; Because of it has great skin effect and bulk effect; Demonstrate the physicochemical properties of a series of uniquenesses at aspects such as magnetic, thermal resistance, interior pressure, light absorption, chemisms, all have broad application prospects in many fields such as magnetic material, catalyst, battery material, coating material, carbide alloy binding agents.Because technical reason, at present, China also can't make extra-fine nickel powder, needs a large amount of imports.
At present, the method for preparing nickel powder both at home and abroad mainly contains several kinds of hydroxyl nickel thermal decomposition method and liquid phase reductions etc.It is more that liquid phase reduction prepares nickel powder research, but the nickel powder of preparation often contains moisture thus, and the latter understands the nickel simple substance of oxidation tool strong reducing property, and making it can not stable existence, thereby in fact be difficult to make nickel simple substance by liquid phase reduction.
Can know from calculation of thermodynamics, can make elemental metals nickel, i.e. NiCl with hydrogen reducing anhydrous chlorides of rase nickel
2+ H
2=Ni+2HCl.But nickel chloride (NiCl
2) very easily suction, thereby commercial can't buying, can not be as the raw material of preparation elemental metals nickel.Therefore, need be that raw material prepares anhydrous chlorides of rase nickel through doing chloridising by cheap nickel powder (being called for short thick nickel powder) or similar dry oxidation nickel (NiO) powder that particle diameter is big, purity is not high, prepare ultra-fine elemental metals nickel powder more thus.But two difficult problems are arranged here, the one, how thick nickel powder or dry oxidation nickel are converted into anhydrous chlorides of rase nickel as much as possible; The 2nd, how to process extra-fine nickel powder by anhydrous chlorides of rase nickel.
Summary of the invention
In order to address the above problem,The present invention proposes a kind of device and method for preparing the high pure and ultra-fine nickel powder, and this device not only can be used for preparing the high pure and ultra-fine nickel powder, also can be used for preparing the superfine powder of some other metal.
The present invention has mainly proposed a kind of crude metal nickel powder (or thick dry oxidation nickel) efficiently to be converted into anhydrous chlorides of rase nickel, anhydrous chlorides of rase nickel in-situ reducing is become the apparatus and method of high pure and ultra-fine nickel powder again.Here " slightly " one is meant raw material particle size much larger than 1 micron, and two are meant that material purity is not high, greatly about 95-99%.This device not only can be used for preparing extra-fine nickel powder, also can be used for preparing the superfine powder of some other metal.These metals comprise elemental silicon, iron, cobalt, platinum group metal, gold, germanium, molybdenum, tungsten etc.
Technical scheme of the present invention is: a kind of device for preparing the high-purity superfine metal nickel powder, this device comprise source of the gas, gas drying tube, gas mass flow amount controller, seal nipple, first reaction tube, second reaction tube, the 3rd reaction tube, the 4th reaction tube, outer tube, tube furnace, conduit, absorption plant and exhaust gas processing device.
The one end mouth of pipe of said the 4th reaction tube is large diameter horn-like;
Said tube furnace is last lower open-type horizontal pipe stove;
Wherein, said outer tube two ends place said tube furnace through the seal nipple sealing; The large diameter horn-like nose end of said the 4th reaction tube is inserted into the said outer tube from the outlet side; One end of said first reaction tube and three reaction tubes is in inlet end is inserted into the horn-like mouth of pipe of said the 4th reaction tube the said outer tube; Said second reaction tube is inserted into the said outer tube from inlet end; Said source of the gas is connected with an end of said gas mass flow amount controller through said gas drying tube; The other end of said gas mass flow amount controller is connected with the other end of said first reaction tube, second reaction tube, the 3rd reaction tube respectively through said seal nipple; Said absorption plant is connected with the other end of seal nipple with said the 4th reaction tube through conduit, and said exhaust gas processing device is connected with said absorption plant through conduit.
Further, said first reaction tube, second reaction tube, the 3rd reaction tube, the 4th reaction tube and outer tube all adopt quartz to process.
Another object of the present invention provides the technology that said apparatus prepares the superfine metal elemental nickel, specifically may further comprise the steps:
Step 1: oxide and the particle diameter that with particle diameter is raw material crude metal elemental nickel or the thick nickel of 1-300 micron is that the micron inoganic solids chloride of 1-300 is that the mixed of 1:1-10 is even with the ratio of molal quantity, is contained in the quartz boat, said quartz boat placed the position of the end of keeping right of the 3rd reaction tube; At room temperature in the 3rd reaction tube, feeding concentration with 100 mL/min flows is the inert gas more than 99.99%; Keep 0.2-1h, startup tube furnace heating under logical inert gas is when being heated to 650-1000 ℃; Stop logical inert gas; Changing feeding is chlorine or chlorine and the carbon monoxide of 200 mL/min with flow, reacts after 0.5-6 hour, stops logical chlorine; Feed inert gas with 50 mL/min flows, obtain the solid water-free nickel chloride; Wherein, the mass ratio of said chlorine and carbon monoxide is 1:0.2-30; Said inoganic solids chloride is sodium chloride, potassium chloride, calcium chloride or magnesium chloride, ferric trichloride or ferrous chloride;
Step 2: under inert gas atmosphere, start said tube furnace heating; When the temperature that is heated to 700-1000 ℃; Make the volatilization of anhydrous chlorides of rase nickel; Blown inert gas in second reaction tube and the 3rd reaction tube is blown into hydrogen in first reaction tube respectively, and the anhydrous chlorides of rase nickel of volatilization is blown out the 3rd reaction tube by inert gas and gets into the hydrogen that blows out with first reaction tube in the 4th reaction tube and in the 4th reaction tube, meet and react and generate the gas phase nickel powder; Meanwhile; Second reaction tube blows out inert gas further to be accelerated gas phase nickel powder and mist and in the 4th reaction tube, is transferred to the cooling of tubule mouth low-temperature space by the horn mouth high-temperature region, is adsorbed on the tube wall of the 4th reaction tube low-temperature space, and the part gas phase nickel powder that is not cooled enters into absorption plant and exhaust gas processing device processing with mist through conduit; Wherein, the ratio of the gas flow of the feeding of first reaction tube, second reaction tube and the 3rd reaction tube is 1:2-20:2-20;
Step 3: at room temperature remove the nickel powder that is bonded on the 4th reaction tube 10 inwalls with absolute ethanol washing; Nickel powder sinks to the solution bottom; With magnet attracts solution bottom nickel powder, with decant method repeatedly chloride solution is separated with nickel powder, use the absolute ethanol washing nickel powder repeatedly; The treating apparatus processing that also uses the same method obtains the purifying nickel powder.
Further, said inert gas is argon gas, helium or nitrogen.
What further, absorption plant was handled the gas phase nickel powder volatilize on a small quantity in the said step 2 is absolute ethyl alcohol; What said exhaust gas processing device was handled mist is that concentration is the sodium hydroxide solution of 5-20%.
The principle of the inventive method is: with the quartz boat of putting into the 3rd reaction tube behind thick nickel powder (or dry oxidation nickel) and inoganic solids chloride such as the abundant mixing of powder such as sodium chloride or/and potassium chloride; In the 3rd reaction tube, lead to drying chlorine (or drying chlorine adds carbon monoxide) then; Reaction generates anhydrous chlorides of rase nickel about 700 ℃, because inoganic solids chloride such as sodium chloride form eutectic compound (2NaClNiCl with the anhydrous chlorides of rase nickel that reaction generates
2), i.e. Ni+Cl
2+ 2NaCl=2NaClNiCl
2, or NiO+Cl
2+ 2NaCl+CO=2NaClNiCl
2+ CO
2, this makes thick nickel powder (or dry oxidation nickel) do the reduction of chlorination Gibbs free energy, thick nickel powder (or dry oxidation nickel) chlorination conversion ratio improves.The application's research shows, during the chlorination of crude metal nickel, does not add the inoganic solids chloride, and the chlorination rate of nickel is 82%; Add sodium chloride, the chlorination rate of nickel is brought up to about 97%.Eutectic compound (2NaClNiCl
2) fusing point is than NiCl
2Or NaCl is low.Anhydrous NiCl
2Fusing point is 1001 ℃, the anhydrous NiCl that dried chlorination obtains
2Higher temperatures (700-1000 ℃) can the volatilization, the anhydrous chlorides of rase nickel of volatilization with inert gas (like Ar or N
2Deng) blow out the 3rd reaction tube and get in the 4th reaction tube, the hydrogen that in this and first reaction tube, blows out meets, and generates the gas phase nickel powder and react, i.e. NiCl
2+ H
2=Ni+2HCl.Meanwhile, second reaction tube can blow out inert gas (like Ar or N
2Deng).The mixed airflow band that the gas phase nickel powder is blown out by first, second and third reaction tube by the condensation of high-temperature region entering low-temperature space and is bonded on the low temperature wall of the 4th reaction tube.Because anhydrous NiCl in the inert gas
2And H
2Concentration is all very low, strafes to observe under the Electronic Speculum and finds, both react and generate the very little regular cube type superfine metal nickel simple substance of particle diameter.It is very fast to add inert gas flow speed, and it is with above-mentioned superfine metal nickel from high temperature reaction zone rapidly and gets into low-temperature space, grows up so above-mentioned superfine metal nickel has little time sintering, so obtained extra-fine nickel powder.Because chlorination temperature (about 700 ℃) is not high, MgO, Cr in the thick nickel powder
2O
3Not high Deng the chlorination degree.Owing to have only the metal chloride volatility bigger, the metal oxide volatility is much lower than chloride.During high temperature (700-1100 ℃) reduction, blowing down at inert gas (like argon gas or nitrogen), mainly is anhydrous NiCl
2Get into gas phase, and do not have MgO, the Cr of chlorination
2O
3, can not volatilize, thereby volatilization gets into the anhydrous NiCl of gas phase
2Purity is higher.In addition, even a small amount of MgO, Cr
2O
3Formed corresponding chloride; These chlorides can not be become metal simple-substance by hydrogen reducing; When with absolute ethanol washing extra-fine nickel powder mixture, these metal chlorides or be dissolved in absolute ethyl alcohol or swim in ethanol solution top are with magnet attracts container bottom nickel powder; Separate with nickel powder with common salt solid above repeatedly the decant method will swim in ethanol solution, thereby the extra-fine nickel powder purity that obtains is very high.
Particularly, the present invention proposes a kind of tube furnace reaction unit that raw material crude metal powder (or thick anhydrous metal oxide) is converted into the high-purity superfine metal powder.Here " slightly " one is meant raw material particle size much larger than 1um, and two are meant that material purity is not high, greatly about 95-99%.Said apparatus comprises:
The present invention compared with prior art has the following advantages and beneficial effect:
1. the method all processes carries out under anhydrous and no high temperature (being higher than room temperature) air conditions, the extra-fine nickel powder that obtains almost less than and water or air react;
2. the anhydrous chlorides of rase nickel that makes in the method need not to take out reactor, but with its in-situ high temperature volatilization, with inert gas (like Ar or N
2Deng) the anhydrous chlorides of rase nickel of volatilization is blown in the gas phase and hydrogen generation gas-solid/liquid/gas reactions, thereby the preparation of anhydrous chlorides of rase nickel and the reduction of anhydrous chlorides of rase ni-mh are subsequently carried out in same reactor continuously.Reaction unit is simple, and method saves time.
Description of drawings
Fig. 1 is the overall structure sketch map of reaction unit of the present invention.
Fig. 2 is a local enlarged diagram of the present invention.
Among the figure:
1. source of the gas, 2. gas drying tube, 3. gas mass flow amount controller, 4. seal nipple, 5. first reaction tube; 6. second reaction tube, 7. the 3rd reaction tube, 8. quartz boat, 9. tube furnace, 10. the 4th reaction tube; 11. outer tube, 12.L type conduit, 13. absorption plants, 14. exhaust gas processing devices.
The specific embodiment
Below in conjunction with concrete accompanying drawing and embodiment technical scheme of the present invention is further specified.
As illustrated in fig. 1 and 2 for the present invention prepares the device sketch map of high-purity superfine metal nickel powder, this device comprises source of the gas 1, gas drying tube 2, gas mass flow amount controller 3, seal nipple 4, first reaction tube 5, second reaction tube 6, the 3rd reaction tube 7, quartz boat 8, tube furnace 9, the 4th reaction tube 10, outer tube 11, L type conduit 12, absorption plant 13 and exhaust gas processing device 14.
Wherein, an end mouth of pipe of the 4th reaction tube 10 is large diameter horn-like;
Tube furnace 9 is last lower open-type horizontal pipe stove;
The two ends of outer tube 11 are through seal nipple 4 sealings, and outer tube 11 places tube furnace 9; The opening that is of the 4th reaction tube 10 is a trumpet-shaped end and is inserted into the outer tube 11 from the outlet side; One end of first reaction tube 5 and the 3rd reaction tube 7 from inlet end be inserted into the 4th reaction tube 10 outer tube 11 be opening be horn-like in; One end of second reaction tube 6 is inserted into the outer tube 11 from inlet end; Source of the gas 1 is connected with gas mass flow amount controller 3 through gas drying tube 2; Gas mass flow amount controller 3 is tightly connected with first reaction tube 5, second reaction tube 6 and the 3rd reaction tube 7 other ends respectively through seal nipple 4; Absorption plant 13 is tightly connected through conduit 12 and seal nipple 4 and the 4th reaction tube 10, and exhaust gas processing device 14 is connected with absorption plant 13 through conduit 12.
With the thick nickel powder of particle diameter 0.050-0.057 millimeter 1.0 g and with particle diameter 0.050-0.100 millimeter 1.62 g MgCl
2Dried powder mixes in the quartz boat shown in Figure 18 of packing into.At room temperature in the 3rd reaction tube 7, led to 100 mL/min high-purity argon gas 30 minutes.Under the 3rd reaction tube 7 logical argon gas conditions, tube furnace 9 is warming up to 900 ℃, again 100 mL/min argon gas were switched to 200 mL/min chlorine reactions 2 hours.Then 200 mL/min chlorine are switched to 50 mL/min argon gas.Obtain the solid water-free nickel chloride, tube furnace 9 temperature are risen to 750 ℃, in second reaction tube 6, lead to 150 mL/min argon gas simultaneously, in first reaction tube 5, lead to 50 mL/min hydrogen, in the 3rd reaction tube 7, lead to 150 mL/min argon gas.Above argon gas and hydrogen purity are 99.99% above high-purity gas; Tube furnace 9 is lowered the temperature naturally; All anhydrous chlorides of rase nickel all are evaporated completely in the quartz boat 8 through measuring afterwards; At room temperature remove the nickel powder that is bonded on reaction tube 10 inwalls, obtain being insoluble to the nickel powder and the magnesium chloride mixture solution that is dissolved in absolute ethyl alcohol of absolute ethyl alcohol with absolute ethanol washing.Behind the solution left standstill, magnesium chloride is dissolved in the ethanol solution, and nickel powder sinks to the solution bottom; With magnet attracts solution bottom nickel powder, with decant method repeatedly magnesium chloride solution is separated with nickel powder, use the absolute ethanol washing nickel powder repeatedly; Obtain the purifying nickel powder, it is kept in the absolute ethyl alcohol.Find not contain any impurity in the nickel powder through x ray fluorescence (XRF) and transmission electron microscope (TEM) mensuration; With strafing the regular cube that nickel particle that electron microscope (SEM) observes is rule; The length of side overwhelming majority is less than 0.1 micron, and what therefore obtain is the high pure and ultra-fine nickel powder.
Mix in the quartz boat shown in Figure 18 of packing into the thick nickel oxide powder of particle diameter 0.050-0.057 millimeter 1.0 g with particle diameter 0.050-0.100 millimeter 1.99 g NaCl dried powders.At room temperature in the 3rd reaction tube 7, lead to 100 mL/min high-purity argon gas 1h.Under the logical argon gas conditions of the 3rd reaction tube 7, tube furnace 9 is warming up to 1000 ℃, again 100 mL/min argon gas were switched to 200 mL/min (mixing with mass ratio 1:30) chlorine and reaction of carbon monoxide 3.5 hours.Then 200 mL/min chlorine are switched to 50 mL/min argon gas, logical argon gas 3h.
Under logical 50 mL/min argon gas conditions, tube furnace 9 heating are risen to 950 ℃ then.And then in second reaction tube 6, lead to 150 mL/min argon gas, in first reaction tube 5, lead to 50 mL/min hydrogen, in the 3rd reaction tube 7, lead to 150 mL/min argon gas.Above argon gas and hydrogen purity are 99.99% above high-purity gas; Tube furnace 9 is lowered the temperature naturally; All anhydrous chlorides of rase nickel all are evaporated completely in the quartz boat 8 through measuring afterwards; At room temperature remove the nickel powder that is bonded on the 4th reaction tube 10 inwalls, obtain being insoluble to the nickel powder and the common salt solid mixture solution of absolute ethyl alcohol with absolute ethanol washing.Behind the solution left standstill, the common salt solid floats over the ethanol solution top, and nickel powder sinks to the solution bottom; With magnet attracts solution bottom nickel powder, with decant method repeatedly the common salt solid is separated with nickel powder, use the absolute ethanol washing nickel powder repeatedly; Obtain nickel powder, it is kept in the absolute ethyl alcohol.Find not contain any impurity in the nickel powder through x ray fluorescence (XRF) and transmission electron microscope (TEM) mensuration; With strafing the regular cube that nickel particle that electron microscope (SEM) observes is rule; The length of side overwhelming majority is less than 0.1 micron, and what therefore obtain is the high pure and ultra-fine nickel powder.
Embodiment 3
With the thick nickel powder of particle diameter 0.050-0.057 millimeter 1.0 g and with particle diameter 0.050-0.100 millimeter 1.98g CaCl
2Dried powder mixes in the quartz boat shown in Figure 18 of packing into.At room temperature in the 3rd reaction tube 7, lead to 100 mL/min high-purity argon gas 0.2h.Under the 3rd reaction tube 7 logical argon gas conditions, tube furnace 9 is warming up to 850 ℃, again 100 mL/min argon gas were switched to 200 mL/min chlorine reactions 6 hours.Then 200 mL/min chlorine are switched to 50 mL/min argon gas, logical argon gas 6h obtains anhydrous chlorides of rase and receives solid;
Under logical 50 mL/min argon gas conditions, tube furnace 9 is heated to 900 ℃ then.And then in second reaction tube 6, lead to 150 mL/min argon gas, in first reaction tube 5, lead to 50 mL/min hydrogen, in the 3rd reaction tube 7, lead to 150 mL/min argon gas.Above argon gas and hydrogen purity are 99.99% above high-purity gas; Tube furnace 9 is lowered the temperature naturally; All anhydrous chlorides of rase nickel all are evaporated completely in the quartz boat 8 through measuring afterwards; At room temperature remove the nickel powder that is bonded on the 4th reaction tube 10 inwalls, obtain being insoluble to the nickel powder and the calcium chloride mixture solution that is dissolved in absolute ethyl alcohol of absolute ethyl alcohol with absolute ethanol washing.Behind the solution left standstill, calcium chloride is dissolved in the ethanol solution, and nickel powder sinks to the solution bottom; With magnet attracts solution bottom nickel powder, with decant method repeatedly magnesium chloride solution is separated with nickel powder, use the absolute ethanol washing nickel powder repeatedly; Obtain the purifying nickel powder, it is kept in the absolute ethyl alcohol.Find not contain any impurity in the nickel powder through x ray fluorescence (XRF) and transmission electron microscope (TEM) mensuration; With strafing the regular cube that nickel particle that electron microscope (SEM) observes is rule; The length of side overwhelming majority is less than 0.1 micron, and what therefore obtain is the high pure and ultra-fine nickel powder.
Mix in the quartz boat shown in Figure 18 of packing into the thick nickel oxide powder of particle diameter 0.050-0.057 millimeter 1.0 g with particle diameter 0.050-0.100 millimeter 2.54g KCl dried powder.At room temperature in the 3rd reaction tube 7, led to 100 mL/min high-purity argon gas 0.5 hour.Under the logical argon gas conditions of the 3rd reaction tube 7, tube furnace 9 is warming up to 1000 ℃, again 100 mL/min argon gas were switched to 200 mL/min (mixing with mass ratio 1:1) chlorine and reaction of carbon monoxide 4 hours.Then 200 mL/min chlorine are switched to 50 mL/min argon gas, logical argon gas 6h obtains anhydrous chlorides of rase nickel solid;
Under logical 50 mL/min argon gas conditions, tube furnace 9 is heated to 700 ℃ then.And then in second reaction tube 6, lead to 150 mL/min argon gas, in first reaction tube 5, lead to 50 mL/min hydrogen, in the 3rd reaction tube 7, lead to 150 mL/min argon gas.Above argon gas and hydrogen purity are 99.99% above high-purity gas; Tube furnace 9 is lowered the temperature naturally; All anhydrous chlorides of rase nickel all are evaporated completely in the quartz boat 8 through measuring afterwards; At room temperature remove the nickel powder that is bonded on the 4th reaction tube 10 inwalls, obtain being insoluble to the nickel powder and the solid potassium chloride mixture solution of absolute ethyl alcohol with absolute ethanol washing.Behind the solution left standstill, solid potassium chloride floats over ethanol solution top, and nickel powder sinks to the solution bottom, and nickel powder bottom magnet attracts solution separates solid potassium chloride with decant method repeatedly with nickel powder, obtain nickel powder, and it is kept in the absolute ethyl alcohol.Find not contain any impurity in the nickel powder through x ray fluorescence (XRF) and transmission electron microscope (TEM) mensuration; With strafing the regular cube that nickel particle that electron microscope (SEM) observes is rule; The length of side overwhelming majority is less than 0.1 micron, and what therefore obtain is the high pure and ultra-fine nickel powder.
Claims (5)
1. device for preparing the high-purity superfine metal nickel powder; It is characterized in that this device comprises source of the gas (1), gas drying tube (2), gas mass flow amount controller (3), seal nipple (4), first reaction tube (5), second reaction tube (6), the 3rd reaction tube (7), the 4th reaction tube (10), outer tube (11), tube furnace (9), L shaped conduit (12), absorption plant (13) and exhaust gas processing device (14);
The one end mouth of pipe of said the 4th reaction tube (10) is large diameter horn-like;
Said tube furnace (9) is last lower open-type horizontal pipe stove;
Wherein, said outer tube (11) two ends are through said seal nipple (4) sealing, and said outer tube (11) places said tube furnace (9); The large diameter horn-like nose end of said the 4th reaction tube (10) is inserted into said outer tube (11) inside from the outlet side; One end of said first reaction tube (5) and three reaction tubes (7) is inserted in the horn-like mouth of pipe of said the 4th reaction tube (10) in the said outer tube (11) from inlet end; Said second reaction tube (6) is inserted into said outer tube (11) inside from inlet end
Said source of the gas (1) is connected with said gas mass flow amount controller (3) through said gas drying tube (2); Said gas mass flow amount controller (3) is connected with the other end of said first reaction tube (5), second reaction tube (6), the 3rd reaction tube (7) respectively through said seal nipple (4); Said absorption plant is tightly connected through the other end of L type conduit (12) and seal nipple (4) and said the 4th reaction tube (10), and said exhaust gas processing device (14) is connected with said absorption plant (13) through L type conduit (12).
2. a device for preparing the high-purity superfine metal nickel powder is characterized in that, said first reaction tube (5), second reaction tube (6), the 3rd reaction tube (7), the 4th reaction tube (10) and outer tube (10) all adopt quartz to process.
3. one kind prepares the technology of superfine metal elemental nickel according to the said device of claim 1, it is characterized in that, specifically may further comprise the steps:
Step 1: oxide and the particle diameter that with particle diameter is raw material crude metal elemental nickel or the thick nickel of 1-300 micron is that the micron inoganic solids chloride of 1-300 is that the mixed of 1:1-10 is even with the ratio of molal quantity, is contained in the quartz boat, said quartz boat placed the position of the end of keeping right of the 3rd reaction tube; At room temperature in the 3rd reaction tube, feeding concentration with 100 mL/min flows is the inert gas more than 99.99%; Keep 0.2-1h, startup tube furnace heating under logical inert gas again is when being heated to 650-1000 ℃; Stop logical inert gas; Changing feeding is chlorine or chlorine and the carbon monoxide of 200 mL/min with flow, reacts after 0.5-6 hour, stops logical chlorine; Feed inert gas with 50 mL/min flows, obtain the solid water-free nickel chloride; Wherein, the mass ratio of said chlorine and carbon monoxide is 1:0.2-30, and said inoganic solids chloride is sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferric trichloride or ferrous chloride;
Step 2: blown inert gas in second reaction tube and the 3rd reaction tube respectively; In first reaction tube, be blown into hydrogen; The anhydrous chlorides of rase nickel of volatilization is blown out the 3rd reaction tube by inert gas and gets into the hydrogen that blows out with first reaction tube in the 4th reaction tube and in the 4th reaction tube, meet and react and generate the gas phase nickel powder; Meanwhile; Second reaction tube blows out inert gas further to be accelerated gas phase nickel powder and mist and in the 4th reaction tube, is transferred to the cooling of tubule mouth low-temperature space by the horn mouth high-temperature region, obtains
The high pure and ultra-fine nickel powderBe adsorbed on the tube wall of the 4th reaction tube low-temperature space, the gas phase composition and the mist that are not adsorbed enter into absorption plant and exhaust gas processing device through conduit; Wherein, the ratio of the gas flow of the feeding of first reaction tube, second reaction tube and the 3rd reaction tube is 1:2-20:2-20;
Step 3: at room temperature remove the nickel powder that is bonded on the 4th reaction tube with absolute ethanol washing; Nickel powder sinks to the solution bottom; With magnet attracts solution bottom nickel powder, with decant method repeatedly chloride solution is separated with nickel powder, use the absolute ethanol washing nickel powder repeatedly; The treating apparatus processing that also uses the same method obtains the purifying nickel powder.
4. technology according to claim 3 is characterized in that, specifically may further comprise the steps, and said inert gas is argon gas, helium or nitrogen.
5. technology according to claim 3 is characterized in that, what absorption plant was handled the gas phase nickel powder volatilize on a small quantity in the said step 2 is absolute ethyl alcohol; What said exhaust gas processing device was handled mist is that concentration is the sodium hydroxide solution of 5-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210268925.5A CN102764895B (en) | 2012-07-30 | 2012-07-30 | Device and method for preparing high-purity ultrafine nickel powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210268925.5A CN102764895B (en) | 2012-07-30 | 2012-07-30 | Device and method for preparing high-purity ultrafine nickel powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102764895A true CN102764895A (en) | 2012-11-07 |
| CN102764895B CN102764895B (en) | 2014-04-16 |
Family
ID=47092590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210268925.5A Expired - Fee Related CN102764895B (en) | 2012-07-30 | 2012-07-30 | Device and method for preparing high-purity ultrafine nickel powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102764895B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498059A (en) * | 2013-09-04 | 2014-01-08 | 昆明理工大学 | Method for making high-purity nickel by chlorination of electrolytic nickel |
| CN105043102A (en) * | 2015-04-16 | 2015-11-11 | 重庆大学 | Novel device and method for reducing sinter using hydrogen |
| CN107116228A (en) * | 2017-06-20 | 2017-09-01 | 中南大学 | A kind of method that solid phase reduction prepares extra-fine nickel powder |
| CN109269302A (en) * | 2018-11-09 | 2019-01-25 | 济南大学 | A kind of calcining vessel and method for calcinating |
| CN109336166A (en) * | 2018-11-21 | 2019-02-15 | 上海谦懋纺织科技有限公司 | A kind of manufacturing device and manufacturing method of efficient deodorizing porous zinc bloom nanometer cylinder |
| CN112974822A (en) * | 2021-02-08 | 2021-06-18 | 天津大学 | Preparation method of cotton-shaped metal nickel powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008045202A (en) * | 2006-08-18 | 2008-02-28 | Korea Inst Of Science & Technology | Method for producing metal nanopowder using gas-phase reaction method |
| CN202254801U (en) * | 2011-07-13 | 2012-05-30 | 沈少波 | Tubular reaction furnace and chlorination reaction device with same |
-
2012
- 2012-07-30 CN CN201210268925.5A patent/CN102764895B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008045202A (en) * | 2006-08-18 | 2008-02-28 | Korea Inst Of Science & Technology | Method for producing metal nanopowder using gas-phase reaction method |
| CN202254801U (en) * | 2011-07-13 | 2012-05-30 | 沈少波 | Tubular reaction furnace and chlorination reaction device with same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498059A (en) * | 2013-09-04 | 2014-01-08 | 昆明理工大学 | Method for making high-purity nickel by chlorination of electrolytic nickel |
| CN103498059B (en) * | 2013-09-04 | 2015-04-22 | 昆明理工大学 | Method for making high-purity nickel by chlorination of electrolytic nickel |
| CN105043102A (en) * | 2015-04-16 | 2015-11-11 | 重庆大学 | Novel device and method for reducing sinter using hydrogen |
| CN105043102B (en) * | 2015-04-16 | 2017-02-22 | 重庆大学 | Novel method for reducing sinter using hydrogen |
| CN107116228A (en) * | 2017-06-20 | 2017-09-01 | 中南大学 | A kind of method that solid phase reduction prepares extra-fine nickel powder |
| CN109269302A (en) * | 2018-11-09 | 2019-01-25 | 济南大学 | A kind of calcining vessel and method for calcinating |
| CN109336166A (en) * | 2018-11-21 | 2019-02-15 | 上海谦懋纺织科技有限公司 | A kind of manufacturing device and manufacturing method of efficient deodorizing porous zinc bloom nanometer cylinder |
| CN112974822A (en) * | 2021-02-08 | 2021-06-18 | 天津大学 | Preparation method of cotton-shaped metal nickel powder |
| CN112974822B (en) * | 2021-02-08 | 2021-12-10 | 天津大学 | Preparation method of cotton-shaped metal nickel powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102764895B (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102764895B (en) | Device and method for preparing high-purity ultrafine nickel powder | |
| CN103482628B (en) | The preparation method of fibrous nano silicon | |
| CN104495908B (en) | Cuprous sulfide raw powder's production technology and cuprous sulfide powder body | |
| Yuan et al. | A solid-state reaction route to prepare LaB6 nanocrystals in vacuum | |
| CN103695691B (en) | A kind of method preparing refractory foam metal tungsten | |
| CN102583398B (en) | Method for preparing silicon dioxide-clad carbon nanotubes and silicon dioxide nanotubes | |
| CN109415207A (en) | The manufacturing device of metal oxide and the manufacturing method of aforementioned metal oxides | |
| CN107523702B (en) | A kind of method that the pressure oxidation of sodium salt system prepares sodium pyroantimonate | |
| CN108383144A (en) | A kind of sponge structure γ-Al2O3Material and preparation method thereof | |
| CN109748318A (en) | A kind of preparation method of stannous sulfide | |
| CN107640751A (en) | One-dimensional boron nitride nano material and preparation method thereof | |
| CN106744730A (en) | Gallium oxide, gallium nitride nano-powder are prepared by raw material two-step method of gallium | |
| CN107673318B (en) | Boron nitride nanotubes and batch preparation method thereof | |
| Mo et al. | Solid-state reaction synthesis of boron carbonitride nanotubes | |
| Sun et al. | Preparation of high purity MoO3 through volatilization of technical-grade Mo calcine in water vapor atmosphere | |
| CN107442130B (en) | A kind of palygorskite load type national standard method and its preparation method and application | |
| CN109574014B (en) | B4C fiber felt and preparation method thereof | |
| Cheng et al. | Preparation of aluminum borate nanowires | |
| CN107604385B (en) | The preparation method of magnesium-rare earth alloy electrolysis raw material | |
| CN105710390A (en) | Method for preparing nano-grade molybdenum powder by directly utilizing industrial-grade molybdenum trioxide | |
| CN103030120B (en) | Fabrication method of boron-carbon-nitrogen nanotube | |
| CN104071760A (en) | Preparation method of porous rod-like hexagonal boron nitride ceramic material | |
| CN102070196A (en) | Method for preparing manganese dioxide nano rod at low temperature | |
| Lu et al. | Top-down synthesis of sponge-like Mn 3 O 4 at low temperature | |
| CN106495113B (en) | The preparation method of high-purity zinc phosphide |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140416 Termination date: 20180730 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |