CN1313232C - Method and device for producing metal powder - Google Patents
Method and device for producing metal powder Download PDFInfo
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- CN1313232C CN1313232C CNB038124017A CN03812401A CN1313232C CN 1313232 C CN1313232 C CN 1313232C CN B038124017 A CNB038124017 A CN B038124017A CN 03812401 A CN03812401 A CN 03812401A CN 1313232 C CN1313232 C CN 1313232C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1286—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using hydrogen containing agents, e.g. H2, CaH2, hydrocarbons
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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
- B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract
Raw metal is intermittently and continuously charged into a chlorination furnace, the raw metal and chlorine gas are reacted in the chlorination furnace to continuously generate metal chloride vapor, and the metal chloride vapor and hydrogen gas are reacted in a reduction furnace to continuously obtain metallic powder. Furthermore, the chlorination furnace in which the chlorination reaction is proceeding is weighed, and the charged amount of the raw metal to the chlorination furnace is controlled depending on the weighing result.
Description
Technical field
The present invention relates to the manufacture method and the manufacturing installation of metal dust, particularly relate to the manufacture method and the manufacturing installation of the metal dusts such as nickel of various uses such as the grafting material of conductive paste filler that electronic units such as being suitable for multi-layer ceramic capacitor etc. uses, titanium material and catalyst.
Background technology
Metal dust such as nickel, copper is widely used in all spectras such as electronic material and catalyst, and particularly average grain diameter is that the following metal dust that is called as the ultra micro powder of 1 μ m has received concern in recent years, and it is used to form the internal electrode of multi-layer ceramic capacitor.In the past, base metal powder such as noble metal powder such as silver, palladium, platinum, gold or nickel, cobalt, iron, molybdenum, tungsten was used for the conductive paste that electronic material is used always, particularly the internal electrode of multi-layer ceramic capacitor.Usually, the structure of multi-layer ceramic capacitor is that dielectric ceramics layer and alternately overlapping as the metal level of internal electrode use is connecting the outer electrode that is connected with the metal level of internal electrode at the two ends of dielectric ceramics layer.Here, as constituting dielectric material, use with the material of the high material of capacitivity such as barium titanate, strontium titanates, yittrium oxide as principal component.On the other hand, metal as constituting internal electrode uses described noble metal powder or base metal powder, recently owing to need more cheap electronic material, utilize the exploitation of the multi-layer ceramic capacitor of latter's base metal powder to prevail, nickel by powder is representative especially.
Multi-layer ceramic capacitor is, dielectric medium powder such as barium titanate is mixed and outstanding turbid with organic bond, adopt the scraper plate method to make it be shaped to sheet, make dielectric raw cook (green sheet), on the other hand, the metal dust that internal electrode is used mixes formation metal dust cream with organic compounds such as organic solvent, plasticizer, organic bonds, adopt silk screen print method that it is printed on the described raw cook.It is laminated to hundreds of layers, then, is firing more than 1000 ℃, last at the two ends of dielectric ceramics layer sintering outer electrode, obtain multi-layer ceramic capacitor.
In the manufacture method of described multi-layer ceramic capacitor, when the operation of organic principle or sintering circuit are thereafter removed in metal cream evaporation, because metal dust expands or shrinks, Volume Changes takes place.On the other hand, Volume Changes also takes place because of sintering in dielectric self equally.That is, owing to while these different materials of sintered dielectric and metal dust, unavoidably the Volume Changes of various materials expansions or contraction causes the sintering behavior difference in sintering process, and the result causes the layer structure destruction of so-called delaminations such as chapping or peel off.
In addition, follow the miniaturization of capacitor, big electric capacityization, according to requirements such as the thin layerization of high laminationization, internal electrode and low resistanceizations, it is below the 1 μ m that the metal dust that uses as internal electrode requires particle diameter certainly, more wishes it is the following ultra micro powder of particle diameter 0.5 μ m.At this moment, owing to there being the meal that 1 μ m is above or 2 μ m are above, it is difficult that the thin layerization of internal electrode becomes, concavo-convex owing to taking place at electrode surface in addition, becomes the reason of short circuit, and the result becomes the reason of delamination.
As the method for making the few metal dust of this meal, the spy opens the manufacture method that discloses a kind of metal dust in the flat 10-219313 communique, and this method comprises following operation: make Metal Contact chlorine, produce the chloride process of metal chloride steam continuously; The metal chloride steam that produces at chloride process is contacted, continuously the muriatic reduction operation in reducing metal with reducibility gas.
Described manufacture method stable, efficiently make the nickel by powder below the 1 μ m particularly aspect, be good method.But the metal dust of generation contains the meal that 1 μ m is above or 2 μ m are above, therefore wishes to improve manufacture method or device, can control the generation of this meal.
Summary of the invention
The object of the invention is to provide a kind of makes feed metal and chlorine reaction generate the metal chloride steam, and this metal chloride steam and hydrogen reaction are obtained in the method for metal dust, there is not meal to produce, particle diameter is stable, particularly average grain diameter is below the 1 μ m, is suitable for the manufacture method and the manufacturing installation of metal dust of the internal electrode of multi-layer ceramic capacitor.
The inventor found that unreacted chlorine in the chlorination furnace is supplied with reduction furnace, thereby cause reaction temperature to rise in order to reach the concentrated repeatedly research of described purpose, is the reason that produces meal.
The manufacture method of metal dust of the present invention is based on that described discovery finishes, this manufacture method is a base feed metal intermittently or continuously in chlorination furnace, make feed metal and chlorine at the chlorination furnace internal reaction, generate the metal chloride steam continuously, make metal chloride steam and hydrogen at the reduction furnace internal reaction, obtain the producing method for metal powder of metal dust continuously, it is characterized in that, monitor the chlorination furnace in the chlorination reaction weight pace of change and when finding the sign of pace of change rapid drawdown, temporarily increase the quantity delivered of described feed metal in the described chlorination furnace suddenly.
In addition, metal powder manufacturing device of the present invention is characterised in that, possesses the raw material feeding funnel that is used for the base feed metal, chlorination is by the chlorination furnace of the feed metal of this raw material feeding funnel supply, reduction furnace with the metal chloride steam that in this chlorination furnace, produces of reduction, raw material feeding funnel and chlorination furnace are communicated with the raw material supplying pipe by the valve that is used for the base feed metal and controls quantity delivered, the carrier pipe that chlorination furnace and reduction furnace use the metal chloride steam that will produce in the chlorination furnace to flow to reduction furnace is communicated with, chlorination furnace possesses the chlorine supply pipe that is used for to internal feed chlorine, reduction furnace possesses the nozzle to inside ejection metal chloride steam, be used for hydrogen supply pipe to internal feed hydrogen, the refrigerating gas supply pipe that is used for the inert gas of the metal dust cooling after internal feed will reduce, and possesses the meausring apparatus of weighing chlorination furnace overall weight, when finding the sign of pace of change rapid drawdown, temporarily increase the control device of the quantity delivered of feed metal in the chlorination furnace suddenly with the pace of change of the weight that monitors the described chlorination furnace in the chlorination reaction.
According to the present invention, owing to control the quantity delivered of feed metal according to the weighing result of chlorination furnace overall weight, so can in chlorination furnace, fill an amount of feed metal.Thus, the reaction homogenising of feed metal and chlorine can reduce the unreacted chlorine of supplying with reduction furnace.
Metal dust of the present invention is to can be used for the internal electrode of multi-layer ceramic capacitor or the metal of catalyst, is noble metals such as silver, palladium, platinum, gold, perhaps base metals such as nickel, cobalt, iron, molybdenum, tungsten.Wherein, base metal is preferred aspect cheap, wherein more preferably nickel.
The particle proterties of the metal dust of making about the present invention, as long as just have no particular limits as various uses is no problem, the occasion that is used for the internal electrode of multi-layer ceramic capacitor, the average grain diameter of preferred use metal dust is 0.01～1 μ m, more preferably 0.1～1 μ m, the particulate of preferred especially 0.1～0.5 mu m range.In addition, the specific area of the BET of metal dust is preferably 1～20m
2/ g.In addition, in order to improve sintering characteristic or dispersiveness, the shape of particle of metal dust wishes it is spherical.
The present invention is to make feed metal and chlorine reaction in chlorination furnace, generate the metal chloride steam continuously, in reduction furnace, make this metal chloride steam and hydrogen reaction, obtain of the invention of the method (below, be sometimes referred to as " chlorination reducing process ") of metal dust continuously for the basis.Generally make in the process of metal dust by the vapour phase reduction reaction this, generate metallic atom in the moment that the metal chloride steam contacts with hydrogen, metallic atom collides each other, aggegation, thereby generates ultramicron, and grows up.And, according to conditions such as the dividing potential drop of the metal chloride steam in the reduction furnace and temperature, the particle diameter of the metal dust that decision generates.In this chlorination reducing process, because generation corresponding to the metal chloride steam of chlorine quantity delivered, therefore by the quantity delivered of control chlorine, can be controlled the amount of the metal chloride steam of supplying with to reduction furnace.In addition, the metal chloride steam produces by the reaction of chlorine and metal, thereby different with the method that produces the metal chloride steam by the muriatic heating evaporation of solid metal, the use of carrier gas not only can be reduced, and carrier gas can be do not used according to creating conditions.Therefore, the reduction of reduction by the carrier gas use amount and the heat energy that accompanies with it can reduce manufacturing cost.
In addition, by mixed inert gas in the metal chloride steam that produces in chlorination reaction, can control the dividing potential drop of metal chloride steam in the reduction furnace.Like this,, can control the particle diameter of metal dust, can make the particle diameter of metal dust stable, can at random set particle diameter simultaneously by the quantity delivered of controlling chlorine or the dividing potential drop of supplying with the metal chloride steam of reduction furnace.
As mentioned above, the chlorination reducing process is obtaining aspect the metal dust of stabilised in size, and have superiority aspect the metal dust can high-efficiency and low-cost ground making.But when making metal dust continuously with the chlorination reducing process, the chlorination reaction velocity in the chlorination furnace changes sometimes.The occasion that chlorination reaction velocity changes, the generating capacity change of the metal chlorination steam that produces in the chlorination furnace, therefore the dividing potential drop of the metal chloride in the reduction furnace changes, and the granularity instability of the metal dust that the result generates can not get the metal dust of required particle diameter sometimes.When particularly making the nickel by powder that the internal electrode of multi-layer ceramic capacitor uses, when the change of this chlorination reaction velocity takes place, produce the meal that 1 μ m is above or 2 μ m are above sometimes in a large number.
For example, make the occasion of nickel by powder, the pill shape raw material nickel of filler mm then is heated to about 800 ℃ in chlorination furnace, supplies with chlorine and raw material nickel thereafter continuously, carries out chlorination reaction.At this moment, raw material nickel is chlorinated, and forms the nickel chloride steam, and the packed layer of the raw material nickel in the chlorination furnace constantly reduces.At this moment, if raw material nickel packed layer reduces along the constant cross-section of chlorination furnace ground, then chlorination reaction velocity keeps constant.
But the temperature distributing disproportionation of the raw material nickel packed layer in the chlorination furnace is even, and according to the position of the chlorine of supplying with in chlorination furnace or the position of raw material nickel, the central authorities of raw material nickel packed layer or peripheral part are by optionally chlorination and minimizing sometimes.When this uneven raw material nickel packed layer continues to reduce, the gap of size to a certain degree of this packed layer appears running through, and the part of the chlorine of supply can not contact with raw material nickel, directly supplies with reduction furnace with the nickel chloride steam.Like this, when unreacted chlorine was directly supplied with reduction furnace, the dividing potential drop of the nickel chloride steam in the reduction furnace reduced, because chlorine supplies in reduction reaction, and the formation speed of nickel by powder rises, meal increases unusually as a result simultaneously.
Discoveries such as the inventor, the maximum reason that meal takes place are that the unreacted chlorine in this chlorination reaction flows into reduction furnace.If original continuous and quantitative was by can detecting this anomaly steam and the forming of gas that chlorination furnace produces, be the mist of chlorine and metal chloride but resemble the present invention, so it separate and quantitative difficulty.
Because chlorination reaction velocity is corresponding with the pace of change of chlorination furnace weight, so monitor that the pace of change of chlorination furnace weight comes the FEEDBACK CONTROL chlorination reaction velocity better.Control device as chlorination reaction velocity, the occasion that reaction speed reduces, mainly such as described, cause that it is main cause that unreacted chlorine flows out because the gap of perforation appears in the feed metal packed layer in the chlorination furnace, therefore have and reduce the amount of chlorine of supplying with chlorination furnace or limit the methods such as quantity delivered of metal chloride steam in reduction furnace that produces by chlorination furnace.But, these methods probably can make the productivity ratio of whole metal dust reduce, and the reaction in the reduction furnace is inhomogeneous, generates the granularity instability of metal dust, therefore preferred in chlorination furnace the base feed metal gap of the feed metal packed layer in the chlorination furnace is eliminated.Usually, when continuous operation, feed metal is supplied with chlorination furnace continuously or intermittently, even but in this case, also detect reaction speed when low, correspondingly wish to increase the quantity delivered of feed metal.
In addition, in chlorination furnace, do not contact as mentioned above, when chlorine just flows directly into reduction furnace with unreacted state with feed metal, the reaction speed rapid drawdown of chlorination reaction, if let go unchecked like this, the granularity instability of the metal dust of Sheng Chenging sometimes, and produce a large amount of meal.
Therefore, in the present invention, wish to monitor the pace of change of chlorination furnace weight, when confirming that pace of change has the sign of rapid drawdown, temporarily increase the quantity delivered of feed metal suddenly.For example, as shown in Figure 4, when detecting the rapid drawdown P of pace of change, one or many is supplied with the maybe above amount of this amount of the amount identical with the feed metal of intermittently or continuously supplying with 30 minutes, and its after image is the same usually, and perhaps decrement intermittently or is continuously supplied with a little.In view of the above, owing to can eliminate the too much state of chlorine by a gas, thereby can reduce the chlorine that unreacted is just supplied with reduction furnace, make the particle size stable of the metal dust that obtains, particularly can suppress the generation of meal.
The preferred specifically force cell (load cell) of the meausring apparatus of chlorination furnace weight especially preferably can be in time through detecting the device of weight change.In the present invention, detect the variation of chlorination stove weight, obtain the weight change of time per unit thus, it is controlled as reaction speed.That is to say that this reaction speed is the weight of the time per unit of the metal chloride steam that produces, constant if this reaction speed always keeps, then chlorination reaction is stable, and the reaction of result in reduction furnace is also stable, and the granularity of the metal dust that obtains is also stable.
In addition, as mentioned above, continuously or intermittently the occasion of base feed metal in chlorination furnace for the raw material feeding funnel of storage and base feed metal, is also used its weight of force cell (loadcell) weighing.Like this, can be by weight change and the weight change detection of chlorination furnace and the reaction speed of control chlorination reaction of raw material feeding funnel.
Below provide the scheme of preferable production process among the present invention.
(1) feed metals such as metallic nickel is supplied with the chlorination furnace that possesses force cell weighing device by the raw material feeding funnel that possesses force cell weighing device, form feed metal packed layer with height to a certain degree.
(2) heat chlorination furnace thereafter, in chlorination furnace, supply with chlorine, the beginning chlorination reaction.
(3) base feed metal continuously or intermittently simultaneously.
(4) detect the reaction speed of chlorination reaction continuously by the weight change of raw material feeding funnel and chlorination furnace.
(5) find that reaction speed changes, when particularly reducing, the quantity delivered that increases feed metal is to reach the reaction speed of regulation.
In addition, in described scheme, more preferably: raw materials weighing feeding funnel weight and chlorination furnace weight, the reaction speed that detects chlorination reaction changes, and automatically controls the quantity delivered of feed metal with it linkedly, the manufacturing system of the metal dust of control reaction speed.
Device of the present invention, as mentioned above, chlorination furnace is configured in the upstream side of reduction furnace, by direct binding chlorination furnace and reduction furnace, can simultaneously and carry out chlorination reaction and reduction reaction continuously, but metal dust is made on excellent in efficiency ground.In addition, owing to produce metal chloride steam with the corresponding amount of the quantity delivered of chlorine in chlorination furnace, and chlorination furnace and reduction furnace directly link, and therefore by the quantity delivered of control chlorine, can control the amount of the metal chloride steam of supplying with to reduction furnace.
In addition, by the inert gas supply pipe is set on chlorination furnace, can be from chlorination furnace, supplying with inert gas here, thereby can control the dividing potential drop of metal chloride steam in the reduction furnace.Therefore, the dividing potential drop of quantity delivered by control chlorine or the metal chloride steam supplied with to reduction furnace can be controlled the particle diameter of metal dust.In addition,, therefore can detect the variation of reaction speed in the chlorination reaction owing to possess the meausring apparatus of measuring the chlorination furnace overall weight, by it is controlled, can be so that the particle size stable of the metal dust that arrives particularly suppresses meal and takes place.In addition, because the raw material feeding funnel also possesses the meausring apparatus of gravimetry, can control reaction speed more accurately.
Below, the embodiment of the metal powder manufacturing device that present invention will be described in detail with reference to the accompanying.Chlorination reaction preferably adopts chlorination furnace shown in Figure 15 to carry out.Chlorination furnace 5 is supported by force cell 9.Be provided for storing the raw material feeding funnel 1 with base feed metal 3 on the top of chlorination furnace 5, raw material feeding funnel 1 has been installed feed metal supply valve 4a, 4b by the centre feed metal supply pipe 21 is connected with the top of chlorination furnace 5.Raw material feeding funnel 1 is supported by force cell 2, and force cell 2 is connected with the force cell 9 of chlorination furnace 5.
Upper lateral part at chlorination furnace 5 connects chlorine supply pipe 6, connects inert gas supply pipe 8 in the following side.Heater 7 is set around chlorination furnace 5, connects metal chloride vapor pipe 12 in the following side of chlorination furnace 5.Though chlorination furnace 5 longitudinal types, horizontal type all can, but in order to carry out the solids-gases haptoreaction equably, preferred longitudinal type.In addition, the pars intermedia of raw material supplying pipe 21, chlorine supply pipe 6 and inert gas supply pipe 8 adopts for example to resemble the structure that has retractility and flexibility the bellows, thus the weight of raw materials weighing feeding funnel 1 and chlorination furnace 5 exactly.In addition, filler 11 is set to constitute siege in the bottom of chlorination furnace 5.Filler 11 for example is made of the small pieces of quartz glass etc., and metal chloride steam and inert gas can circulate, and prevent that feed metal from falling.
Chlorine carries out flow measurement and imports from chlorine supply pipe 6 continuously.The preferred quartz glass system of chlorination furnace 5 and miscellaneous part.Metal chloride vapor pipe 12 is connected with the metal chloride steam jetting nozzle 14 of reduction furnace described later 13 upper surfaces.
No matter as the form of the feed metal 3 of initial feed how, from contacting efficiency, prevent that the viewpoint that the pressure loss rises from considering, the about 5mm～20mm's of preferable particle size is granular, block, tabular etc., and in addition, its purity is preferably about more than 99.5%.The height of the feed metal packed layer 10 in the chlorination furnace 5, based on the shape of chlorine feed speed, chlorination furnace temperature, continuous operating time, feed metal 3 etc., the scope that the chlorine that suitably is set in supply fully is transformed into the metal chloride steam gets final product.Temperature in the chlorination furnace 5 is so long as the temperature that feed metal is chlorinated gets final product, and the occasion of metallic nickel is in order fully to react, take more than 800 ℃, the fusing point of nickel is considered the durability of reaction speed and chlorination furnace 5 below 1483 ℃, preferred 900 ℃～1100 ℃ scope in practicality.
In chlorination furnace 5, supply with chlorine continuously by chlorine supply pipe 6, simultaneously by switch raw material supplying valve 4 from raw material feeding funnel 1 base feed metal 3 continuously or intermittently.At this moment, the quantity delivered of feed metal is by force cell 2 weighings.
The metal chloride steam that produces in the chlorination furnace 5, directly be delivered to reduction furnace 13 by metal chloride vapor pipe 12, perhaps according to circumstances mix 1 mole of %～30 mole % from inert gases such as the nitrogen of inert gas supply pipe 8 or argons with respect to the metal chloride steam, with this mixed gas delivery to reduction furnace.The supply of this inert gas becomes the particle diameter governing factor of metal dust.The surplus mixing of inert gas consumes a large amount of inert gases undoubtedly, causes energy loss, and is uneconomical.From this point of view, the preferable alloy chloride vapor dividing potential drop of the mist by carrier pipe 12 in that the stagnation pressure note was done, is preferably 0.5～1.0 scope at 1.0 o'clock, particularly make the occasion of the small particle diameter metal dust of particle diameter 0.15 μ m～0.5 μ m, preferred dividing potential drop about 0.6～0.9.And as mentioned above, metal chloride steam generating capacity can be adjusted arbitrarily by the chlorine quantity delivered, and in addition, the dividing potential drop of metal chloride steam also can be adjusted arbitrarily by the inert gas quantity delivered.
The metal chloride steam that produces in the chlorination furnace 5 is delivered to reduction furnace 13 continuously.In the upper end of reduction furnace 13, the metal chloride steam jetting nozzle 14 (being designated hereinafter simply as nozzle 14) that is connected with metal chloride vapor pipe 12 is outstanding downwards.In addition, connect hydrogen supply pipe 15, connect refrigerating gas supply pipe 17 in the following side of reduction furnace 13 in the upper surface of reduction furnace 13.In addition, heater 16 is set around reduction furnace 13.Nozzle 14 has from chlorination furnace 5 and sprays the metal chloride steam function of (containing inert gas sometimes) with desirable flow velocity in reduction furnace 13 as described later.
When carrying out the reduction reaction of metal chloride steam and hydrogen, form the similar reaction flame 18 of extension downwards of burning flame with gaseous fuel such as LPG from the leading section of nozzle 14.Hydrogen quantity delivered in the reduction furnace 13 is the chemical equivalent of metal chloride steam, and is promptly stoichiometric about 1.0～3.0 times of the chlorine of supplying with to chlorination furnace 5, preferably about 1.1～2.5 times, unqualified to this.But, when supplying with hydrogen superfluously, give in the reduction furnace 13 and cause big hydrogen stream, make metal chloride steam discharging jet disorder from nozzle 14, become the uneven reason of reduction reaction, cause the gas that is not consumed to emit simultaneously, uneconomical.In addition, the temperature of reduction reaction is so long as finish that the temperature of sufficient reacting is above to get final product, make the occasion of nickel by powder, owing to generate the nickel by powder processing ease of solid shape, therefore be preferably below the fusing point of nickel, consider reaction speed, the durability of reduction furnace 13, economy, 900 ℃～1100 ℃ is practical, but there is no particular limitation to this.
As mentioned above, the chlorine that imports chlorination furnace 5 becomes in fact the metal chloride steam with mole, with it as the reduction raw material.By adjusting metal chloride steam or metal chloride steam-inert gas mist linear velocity from the air-flow of nozzle 14 front ends ejection, can be so that suitableization of particle diameter of the metal dust that arrives 19.That is, if nozzle diameter is constant, then can be according to chlorine quantity delivered in the chlorination furnace 5 and inert gas quantity delivered, the particle diameter of the metal dust 19 that generates in the reduction furnace 13 is adjusted into target zone.The preferred flow line speed of nozzle 14 front ends (total of metal chloride steam and inert gas (being converted into the calculated value of the gas delivery volume under the reduction temperature)), under 900 ℃～1100 ℃ reduction temperature, be set at about 1m/ second～30m/ second, when making the nickel by powder of small particle diameter of 0.1 μ m～0.3 μ m, about 5m/ second～25m/ is comparatively suitable second, when making the nickel by powder of 0.4 μ m～1.0 μ m, about 1m/ second～15m/ is comparatively suitable second.The direction of principal axis linear velocity of hydrogen in reduction furnace 13 is preferably about 1/50～1/300 of metal chloride steam spouting velocity (linear velocity), is preferably 1/80～1/250.Therefore, become the state that the metal chloride steam sprays to static hydrogen environment from nozzle 14 in fact.In addition, the Way out of hydrogen supply pipe 15 is not preferably towards fire side.
In manufacture method of the present invention, when the chlorine supply flow rate in the increase chlorination furnace 5, the particle diameter of the metal dust 19 that generates in the reduction furnace 13 diminishes, and on the contrary, when reducing the chlorine supply flow rate, particle diameter increases.In addition, near described chlorination furnace 5 outlets, pass through metal chloride steam mixed inert gas is adjusted the dividing potential drop of metal chloride steam, particularly mix with the scope of 1 mole of %～30 mole % with respect to the metal chloride steam, for example when improving dividing potential drop, can increase the particle diameter of the metal dust of generation, on the contrary, when reducing the dividing potential drop of metal chloride steam, the particle diameter of the metal dust that can reduce to generate.
In chlorination furnace 5, carry out chlorination reaction as mentioned above continuously, the metal chloride steam that produces is made in reduction furnace 13 in the process of metal dust, with the weight of force cell 9 weighing chlorination furnaces 5, continuous detecting weight change.On the other hand, by the weight change of force cell 2 consecutive weighings raw material feeding funnels 1, detect the weight of the feed metal of in chlorination furnace 5, supplying with 3.By these in time the weight change of process detect the reaction speed of chlorination reaction.That is to say, weight change addition with the time per unit of the weight change of the time per unit of raw material feeding funnel 1 and chlorination furnace 5, be the weight of the time per unit of the metal chloride steam of generation in the chlorination furnace 5, become the reaction speed (metal chloride steam generating capacity weight/time) of chlorination reaction.
In the process of making metal dust, continue to monitor this reaction speed, when finding that reaction speed has the sign of reduction, the temporary transient quantity delivered that increases from the raw metal 3 of raw material feeding funnel 1 makes reaction speed stable.At this moment because feed metal packed layer 10 top inhomogeneous, preferably at the simultaneously feeding metal of Visual Confirmation so that should above become level and smooth.In addition, be preferably set to the weight change and feed metal supply valve 4 interlocks that utilize scattered control system etc. that force cell 2 and force cell 9 are detected, when the sign of reaction speed reduction occurring, metal supply valve 4 is opened, and base feed metal 3 makes reaction speed stable.
The manufacture method of metal dust of the present invention can be provided with refrigerating work procedure.Refrigerating work procedure as shown in Figure 1, can with reduction furnace 13 in the space segment of nozzle 14 opposition sides carry out, perhaps also can use other containers that are connected with the outlet of reduction furnace 13.In addition, said cooling among the present invention, be meant the operation of carrying out for the growth of the metallic in the air-flow (comprising hydrogen chloride gas) that stops or suppressing to generate by reduction reaction, particularly, be meant that near with the reduction reaction that is through with 1000 ℃ air-flow is cooled to the operation about 400 ℃～800 ℃ rapidly.Certainly, also can be cooled to that following temperature.
As the preferred example that is used to cool off, can adopt the structure that is blown into inert gas from flame front space segment downwards.Particularly, by being blown into nitrogen from refrigerating gas supply pipe 17, can cooling blast.By being blown into inert gas, can prevent the aggegation of metal dust 19, carry out particle diameter control simultaneously.The refrigerating gas supply pipe can at random change cooling condition by being provided with at 1 position or being provided with at a plurality of positions at the above-below direction change location of reduction furnace 13, can carry out particle diameter thus more accurately and control.
Pass through the metal dust 19 of above operation and the mist of hydrogen chloride gas and inert gas and be transported to recovery process, belonged to powder 19 from the mist separating and recovering gold there.When separating recovery, capture the combination more than a kind or 2 kinds that captures in separator, the oil in separator and the magnetic separating device in preference such as bag hose, the water, but be not limited thereto.For example adopt the occasion of bag hose trapping metals powder 19, also the mist of the metal dust 19 that generates in the refrigerating work procedure and hydrogen chloride gas and inert gas can be imported bag hose, only reclaim metal dust 19 after, deliver to washing procedure.In adopting oil, capture the occasion of separating, preferably use the normal paraffin hydrocarbons or the light oil of carbon number 10～18.In adopting water or the occasion that captures in the oil, if in trapping solution, add in the known antioxidants such as the phenols of metal inert agents of surfactants such as polyether polyols, polyoxy propane diols or their derivative (monoalky lether, monoesters) about 10ppm～1000ppm or anhydro sorbitol, anhydro sorbitol monoesters, BTA or derivatives thereof representative or amine more than a kind or 2 kinds, to the anti-aggegation of metal powder particles and antirust effectively.
As mentioned above, manufacture method and manufacturing installation according to the metal dust of former employing chlorination reducing process, can be because the inhomogeneous unreacted chlorine that causes of the feed metal packed layer reaction in the chlorination furnace flows into reduction furnace, therefore the granularity instability of the metal dust that generates has particularly produced oversize grain.But, according to manufacture method of the present invention and manufacturing installation, by the weight of weighing chlorination furnace, the reaction speed that can control chlorination reaction makes it stable, therefore can prevent that unreacted chlorine from flowing into to reduction furnace, the result can make particle size stable, does not particularly have the metal dust of oversize grain.In addition, according to existing method or existing apparatus, as mentioned above owing to instabilities such as chlorination reaction rapid drawdowns, the reaction speed that can not raise, and according to the present invention, because reaction speed is stable, the reaction speed that therefore can raise, the result can improve the productivity ratio of metal dust.
Description of drawings
Fig. 1 is the longitudinal section of structure of the metal powder manufacturing device of expression embodiment of the present invention.
Fig. 2 is the curve map of the size distribution of the nickel by powder made of expression embodiment and comparative example.
Fig. 3 A is the SEM photo of the nickel by powder made of embodiment, and Fig. 3 B is the SEM photo of the nickel by powder made of comparative example.
Fig. 4 is the line chart of the reaction speed (pace of change of chlorination furnace weight) in the expression chlorination furnace.
Symbol description
5 ... chlorination furnace, 9 ... force cell, 1 ... raw material feeding funnel, 2 ... force cell, 13 ... reduction furnace, 3 ... feed metal.
The specific embodiment
Below illustrate in greater detail the present invention by specific embodiment.
Embodiment
In the chlorination furnace 5 of metal powder manufacturing device shown in Figure 1, by the raw material nickel 15kg of raw material feeding funnel 1 filling average grain diameter 5mm, making the furnace inner environment temperature is 1100 ℃, with the flow importing chlorine of 4Nl/min, beginning chlorination reaction.Afterwards, by raw material feeding funnel 1 every 5 minutes with 0.5kg/ intermittently to chlorination furnace 5 base feed nickel.Like this, with the metallic nickel chlorination, produce the nickel chloride steam.
To the nitrogen of 10% (mol ratio) of wherein mixing the chlorine quantity delivered, this nickel chloride steam-nitrogen mixture gas is imported the reduction furnace 13 of the environment temperature that is heated to 1000 ℃ with flow velocity 2.3m/ second (1000 ℃ of conversions) from nozzle 14.Supply with hydrogen from the top of reduction furnace 13 with flow velocity 7Nl/min simultaneously, reduction nickel chloride steam.
As mentioned above, continuous (30 hours) carry out chlorination reaction and reduction reaction concurrently simultaneously, at this moment use the weight of force cell 2 and 9 raw materials weighing feeding funnels 1 and chlorination furnace 5 respectively, detect the reaction speed of the chlorination reaction in the chlorination furnace by its weight change continuously.After making beginning, find that at the 25th hour reaction speed has the sign of reduction, therefore per 1 5kg ground increases the raw material nickel quantity delivered from raw material feeding funnel 1, makes reaction speed stable, continues to make.
The generation gas that comprises the nickel by powder that generates in the reduction reaction mixes the nitrogen cooling in refrigerating work procedure.Then, in pure water, import, separate and reclaim nickel by powder by the mist that nitrogen-salt acid vapour-nickel by powder is formed.Then, behind the nickel by powder with the pure water washing and recycling, drying obtains the goods nickel by powder.The size distribution of the nickel by powder that obtains as shown in Figure 2, in addition, the SEM photo is as shown in Figure 3A.The average grain diameter of BET method is 0.40 μ m, and the average grain diameter when being suspended in organic solvent is 1.50 μ m, and the above meal of other 5 μ m is 0%.Wherein, average grain diameter and size distribution when being suspended in organic solvent, use laser light scattering to draw folding method granulometry machine (CoulterLS230: コ-Le -corporate system), after making an amount of metal dust be suspended in α-terpineol, apply ultrasonic wave, disperseed 3 minutes, and measured for 1.8 times, obtain the size distribution of volume statistical value in the sample refractive index.
Comparative example
The weight of raw materials weighing feeding funnel 1 and chlorination furnace 5 is not controlled the reaction speed of the chlorination reaction in the chlorination furnace, in addition, makes similarly to Example 1.The size distribution of the nickel by powder that obtains as shown in Figure 2, in addition, the SEM photo is shown in Fig. 3 B.The average grain diameter of BET method is 0.45 μ m, and the average grain diameter when being suspended in organic solvent is 1.45 μ m, and the above meal of other 5 μ m is 3.0%.
The size distribution of the nickel by powder of in the embodiment of the inventive method, making, compare with the nickel by powder of comparative example manufacturing as can be seen from Figure 2, particularly meal is few, and see that from the SEM photo of Fig. 3 the meal more than the 1 μ m is more the nickel by powder that comparative example makes, but by comparison, the meal more than the 1 μ m is few in the nickel by powder of embodiment manufacturing.
As described above, manufacture method and manufacturing installation according to metal dust of the present invention, the internal electrode that can make multi-layer ceramic capacitor efficiently etc. requires the metal dusts such as nickel by powder of the fine particle size below the 1 μ m, in addition, can control the reaction speed of chlorination reaction, the result has brought into play can make epigranular, do not have the effect of the metal dust of oversize grain.
Claims (13)
1. the manufacture method of a metal dust, for at base feed metal intermittently or continuously in chlorination furnace, make described feed metal and chlorine at described chlorination furnace internal reaction, generate the metal chloride steam continuously, make described metal chloride steam and hydrogen at the reduction furnace internal reaction, obtain the producing method for metal powder of metal dust continuously, it is characterized in that, monitor the described chlorination furnace in the chlorination reaction weight pace of change and when finding the sign of described pace of change rapid drawdown, temporarily increase the quantity delivered of described feed metal in the described chlorination furnace suddenly.
2. the manufacture method of metal dust according to claim 1 is characterized in that, when finding the sign of described pace of change rapid drawdown, with this sign interlock, temporarily, automatically increases the quantity delivered of feed metal described in the described chlorination furnace suddenly.
3. the manufacture method of metal dust according to claim 1 is characterized in that, adopts force cell to carry out the weight weighing of described chlorination furnace.
4. the manufacture method of metal dust according to claim 1 is characterized in that, the weight of the raw material feeding funnel integral body of described feed metal is supplied with in weighing in described chlorination furnace.
5. the manufacture method of metal dust according to claim 1 is characterized in that, described metal is a nickel.
6. the manufacture method of metal dust according to claim 5 is characterized in that, described metal dust is the nickel by powder of average grain diameter 0.01～1 μ m.
7. the manufacture method of metal dust according to claim 6 is characterized in that, described metal dust is that conductive paste is used.
8. the manufacture method of metal dust according to claim 6 is characterized in that, described metal dust is that multi-layer ceramic capacitor is used.
9. the manufacturing installation of a metal dust is characterized in that, possesses the reduction furnace of the metal chloride steam that the chlorination furnace of the feed metal that the raw material feeding funnel that is used for the base feed metal, chlorination supplied with by this raw material feeding funnel and reduction produce at this chlorination furnace,
Described raw material feeding funnel and described chlorination furnace are communicated with the raw material supplying pipe by the valve that is used for the base feed metal and controls quantity delivered,
The carrier pipe that described chlorination furnace and described reduction furnace use the metal chloride steam that will produce in the chlorination furnace to flow to reduction furnace is communicated with,
Described chlorination furnace possesses the chlorine supply pipe that is used for to internal feed chlorine,
Described reduction furnace possess to inside spray described metal chloride steam nozzle, be used for to internal feed hydrogen the hydrogen supply pipe, be used for the refrigerating gas supply pipe of the inert gas of the metal dust cooling after internal feed will reduce,
And, possess the meausring apparatus of the described chlorination furnace overall weight of weighing and monitor described chlorination furnace weight pace of change and when finding the sign of described pace of change rapid drawdown, temporarily increase the control device of the quantity delivered of feed metal described in the described chlorination furnace suddenly.
10. the manufacturing installation of the metal dust of stating according to claim 9 is characterized in that, described control device with this sign interlock, temporarily, is automatically controlled the quantity delivered of described feed metal in the described chlorination furnace when finding the sign of described pace of change rapid drawdown.
11. the manufacturing installation of metal dust according to claim 9 is characterized in that, possesses the meausring apparatus of the described raw material feeding funnel of weighing overall weight.
12. the manufacturing installation of metal dust according to claim 9 is characterized in that, described meausring apparatus is a force cell.
13. the manufacturing installation of metal dust according to claim 9 is characterized in that, described metal is a nickel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002155101A JP3492672B1 (en) | 2002-05-29 | 2002-05-29 | Metal powder manufacturing method and manufacturing apparatus |
| JP155101/2002 | 2002-05-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1655897A CN1655897A (en) | 2005-08-17 |
| CN1313232C true CN1313232C (en) | 2007-05-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB038124017A Expired - Lifetime CN1313232C (en) | 2002-05-29 | 2003-05-19 | Method and device for producing metal powder |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20050217428A1 (en) |
| EP (1) | EP1508390A4 (en) |
| JP (1) | JP3492672B1 (en) |
| KR (1) | KR100961579B1 (en) |
| CN (1) | CN1313232C (en) |
| TW (1) | TWI229621B (en) |
| WO (1) | WO2003099491A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI381897B (en) * | 2004-12-22 | 2013-01-11 | Taiyo Nippon Sanso Corp | Process for producing metallic ultra fine powder |
| US7833472B2 (en) * | 2005-06-01 | 2010-11-16 | General Electric Company | Article prepared by depositing an alloying element on powder particles, and making the article from the particles |
| KR100830931B1 (en) | 2007-05-23 | 2008-05-22 | (주) 나노기술 | Vacuum type high voltage gap switch by gas vacuum and purging and manufacturing method of metal nano powder by it |
| CN102632245B (en) * | 2012-05-10 | 2014-08-06 | 湖南顶立科技有限公司 | Preparation method of high-purity molybdenum powder |
| EP3360627B1 (en) * | 2017-02-08 | 2022-01-05 | Heraeus Deutschland GmbH & Co. KG | Powder for use in an additive manufacturing method |
| JP7112899B2 (en) * | 2018-06-28 | 2022-08-04 | 東邦チタニウム株式会社 | How to manage metal filling |
| KR102484793B1 (en) * | 2018-06-28 | 2023-01-05 | 도호 티타늄 가부시키가이샤 | Metal powder, manufacturing method thereof, and method for predicting sintering temperature |
| US10612111B2 (en) * | 2018-08-21 | 2020-04-07 | Robert Ten | Method and apparatus for extracting high-purity gold from ore |
| JP6771636B1 (en) * | 2019-11-22 | 2020-10-21 | 東邦チタニウム株式会社 | Copper powder manufacturing method |
| JP6704083B1 (en) * | 2019-11-22 | 2020-06-03 | 東邦チタニウム株式会社 | Copper powder and its manufacturing method |
| CN113351121A (en) * | 2021-06-30 | 2021-09-07 | 蚌埠中瓷纳米科技有限公司 | System and method for continuously conveying solid mixed material into chlorination furnace |
| CN114410967A (en) * | 2022-01-20 | 2022-04-29 | 北京普能世纪科技有限公司 | Method and device for accurately controlling reduction valence state of high-purity vanadium pentoxide |
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| EP0887133A1 (en) * | 1996-12-02 | 1998-12-30 | Toho Titanium Co., Ltd. | Process for the production of metal powder and equipment therefor |
| CN1275103A (en) * | 1998-06-12 | 2000-11-29 | 东邦钛株式会社 | Method for producing metal powder |
| JP2000335905A (en) * | 1999-05-31 | 2000-12-05 | Toho Titanium Co Ltd | Apparatus for chlorinating metal, and method for producing metal chloride |
| EP1114684A1 (en) * | 1999-06-08 | 2001-07-11 | Toho Titanium Co., Ltd. | Method for preparing ultra fine nickel powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4558019A (en) | 1984-01-20 | 1985-12-10 | Allied Corporation | Periclase refractory brick with oxyhydrocarbon component |
| US4588019A (en) * | 1984-04-17 | 1986-05-13 | Wentzell Joseph M | Methods of controlling solidification of metal baths |
| JPH0445207A (en) * | 1990-06-12 | 1992-02-14 | Kawasaki Steel Corp | Manufacture of spherical nickel fine particles |
| US5131634A (en) * | 1991-10-07 | 1992-07-21 | Westinghouse Electric Corp. | Sublimer-reactor system with weighing means |
| JP3504481B2 (en) | 1996-12-02 | 2004-03-08 | 東邦チタニウム株式会社 | Method for producing Ni powder |
-
2002
- 2002-05-29 JP JP2002155101A patent/JP3492672B1/en not_active Expired - Lifetime
-
2003
- 2003-05-19 WO PCT/JP2003/006191 patent/WO2003099491A1/en active Application Filing
- 2003-05-19 EP EP03725825A patent/EP1508390A4/en not_active Withdrawn
- 2003-05-19 US US10/515,952 patent/US20050217428A1/en not_active Abandoned
- 2003-05-19 KR KR1020047018650A patent/KR100961579B1/en active IP Right Grant
- 2003-05-19 CN CNB038124017A patent/CN1313232C/en not_active Expired - Lifetime
- 2003-05-28 TW TW092114329A patent/TWI229621B/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0887133A1 (en) * | 1996-12-02 | 1998-12-30 | Toho Titanium Co., Ltd. | Process for the production of metal powder and equipment therefor |
| CN1275103A (en) * | 1998-06-12 | 2000-11-29 | 东邦钛株式会社 | Method for producing metal powder |
| JP2000335905A (en) * | 1999-05-31 | 2000-12-05 | Toho Titanium Co Ltd | Apparatus for chlorinating metal, and method for producing metal chloride |
| EP1114684A1 (en) * | 1999-06-08 | 2001-07-11 | Toho Titanium Co., Ltd. | Method for preparing ultra fine nickel powder |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040111647A (en) | 2004-12-31 |
| EP1508390A4 (en) | 2007-07-11 |
| JP2004027242A (en) | 2004-01-29 |
| TWI229621B (en) | 2005-03-21 |
| KR100961579B1 (en) | 2010-06-04 |
| CN1655897A (en) | 2005-08-17 |
| WO2003099491A1 (en) | 2003-12-04 |
| EP1508390A1 (en) | 2005-02-23 |
| US20050217428A1 (en) | 2005-10-06 |
| TW200400095A (en) | 2004-01-01 |
| JP3492672B1 (en) | 2004-02-03 |
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