CN101568398A - Direct passivation of metal powder - Google Patents
Direct passivation of metal powder Download PDFInfo
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- CN101568398A CN101568398A CNA2006800567580A CN200680056758A CN101568398A CN 101568398 A CN101568398 A CN 101568398A CN A2006800567580 A CNA2006800567580 A CN A2006800567580A CN 200680056758 A CN200680056758 A CN 200680056758A CN 101568398 A CN101568398 A CN 101568398A
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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
- C22B34/1268—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 alkali or alkaline-earth metals or amalgams
- C22B34/1272—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 alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
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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
Abstract
A method of producing passivated Ti or Ti alloy particles with oxygen concentrations of less than about 900 parts per million (ppm), which includes introducing a halide vapor of Ti or the metal constituents of the alloy at sonic velocity or greater into a stream of liquid alkali or liquid alkaline earth metal or mixtures thereof forming a reaction zone in which the halide is reduced by the liquid metal present in sufficient excess of stoichiometric such that Ti or Ti alloy powder from the reduction of the halide by the liquid metal is friable. After filtration and distillation excess liquid metal is removed fom the Ti or Ti alloy powder that is then maintained at elevated temperature for a time sufficient to grow the particles to average diameters calculated from BET surface area measurement greater than about one micron. After cooling the Ti or Ti alloy powder to temperature of about 800C or less, the cooled Ti or Ti alloy powder is contacted with air and/or water to passivate the particles to produce friable metal powder and to remove other reaction products. A system for accomplishing the method is also shown.
Description
Technical field
The present invention relates to use Armstrong method pan in next life to belong to and alloy.
Background of invention
The present invention relates to use in U.S. Patent No. 6,409,797, No.5,958,106 and No.5,779, disclosed universal method pan in next life belongs to and alloy in 761, and its all patents are incorporated this paper and the preferred method that wherein prepares titanium or titanium alloy by reduction halide in the logistics of reducing metal into.Although method disclosed herein is suitable for for any disclosed hereinafter element or its alloy, the present invention will describe with regard to titanium and alloy thereof, only because the titanium that now can supply in the U.S. is not enough to satisfy the demands.In addition, because by using aforesaid method to reduce the cost of titanium and alloy thereof, thus increase in demand, even surpassed the estimation of aerospace company and Ministry of National Defence.
Titanium is at the very many elements of All Around The World distribution, but it is very expensive, because it is outmoded to produce the required method of titanium.As everyone knows, Kroll method and Hunter method are main methods, worldwide produce titanium by it.These two kinds of methods all are batch technologies, and it at first produces the melted material of titanium and salt and excessive reducing metal (sodium that is used for the magnesium of kroll process and is used for Han Tefa).This melted material (being called sponge) must be removed crushing and the step electrorefining to repeat thereafter then from the container of making it therein.
Described hereinafter the present invention is the improvement of disclosed Armstrong method in the above United States Patent (USP) of incorporating into.
Because titanium is the reactive metal of extreme, and produce by the Armstrong method as very thin powder (have usually as the BET surface area and measure 0.1 micron to 1 micron the average diameter of being calculated), so it is kept at high temperature so that average particulate diameter is brought up to greater than 1 micron thereafter.But, or even also intractable of large diameter powder, unless it is passivated.Passivation means a spot of oxygen is incorporated in the powder, so that form titanium dioxide from the teeth outwards, so that powder does not burn in being exposed to air the time.Too many oxygen will improve oxygen content, surpass the ASTM specification that is used for 2 grades of chemical pure titaniums or is used for 5 grades of titaniums of ASTM, just 6/4 alloy (the % vanadium of the aluminium of 6wt% and 4wt, all the other are titanium).Up to now, unique practical ways of believing the passivation titanium powder is to flow out the inert gas argon gas for example with very little oxygen concentration, the oxygen content that the duration is enough to increase powder surface spontaneous combustion when preventing in being exposed to air.The time that is used for passivation is with a hour metering, and is the large-scale commercial applications Design of device problem that is used for based on continuation method.
Yet, unexpectedly also surprisingly, discovery is under certain condition, the passivation of titanium powder and/or titanium alloy powder can be finished by directly being exposed in air and/or water and/or the salt solution, it has not only reduced passivation time but also has simplified the equipment design, thereby makes this method simpler, more effective and more cheap.
Summary of the invention
Therefore, main purpose of the present invention provides a kind of method of frangible metal powder of production passivation, and unmatchful in the previous demand of long-term passivation.
Another object of the present invention provides the method for producing the passive metal powder, comprise the metal halide steam is incorporated in the logistics of the liquid base metal that forms conversion zone or liquid base earth metal or their mixture, wherein, described halide vapor is reduced by the described liquid metals that exists with abundant excessive stoichiometric proportion, so that reduce the metal dust that described halide vapor obtains by described liquid metals is frangible, from product, separate the most of at least of described excessive liquid metals, described metal dust growth is had greater than about 1 micron until the particle that forms described metal dust measure the average diameter of being calculated by the BET surface area, cool off described metal dust, and the metal dust of cooling directly contact with air and/or water and/or salt solution, so that the passivation metal dust frangible with production.
Another object of the present invention provides a kind of method of producing the passive metal powder, comprise that halide vapor with described metal is incorporated in the logistics of the liquid sodium metal that forms conversion zone or liquid magnesium metal, wherein, by reduce described chloride at the described liquid sodium metal that exists with abundant excessive stoichiometric proportion or liquid magnesium metal, so that the described metal dust that forms by described liquid sodium metal or the described halide vapor of described liquid magnesium metallic reducing is frangible, product and most at least described excessive sodium metal or magnesium metal are separated, described metal dust is at high temperature kept a period of time that is enough to make described powder growth, have greater than about 1 micron and measure the average diameter of being calculated until forming described particles of powder, described metal dust is cooled to be lower than about 100 ℃ by the BET surface area; And the metal dust of described cooling and air and/or water and/or salt solution contacted, so that passivation and produce frangible metal dust.
Another purpose of the present invention provides a kind of production and has the titanium powder of the passivation that is less than the about 1800 parts/oxygen concentration of 1,000,000 parts (ppm) or the method for titanium alloy powder, comprise that halide vapor with the metal ingredient of the halide vapor of titanium or described alloy is incorporated in the logistics of the liquid base metal that forms conversion zone or liquid base earth metal or their mixture, wherein, described halide is reduced by the described liquid metals that exists with abundant excessive stoichiometric proportion, so that reduce Ti powder or the Ti alloy powder that described halide obtains by described liquid metals is frangible, described Ti powder or described Ti alloy powder product are separated with most at least described excessive liquid metals, described Ti powder or described Ti alloy powder at high temperature kept is enough to make the germination that forms described Ti powder or Ti alloy powder to a period of time greater than about 1 micron average diameter of being calculated by the measurement of BET surface area, cool off described Ti powder or described Ti alloy powder, and in the Ti powder of cooling or Ti alloy powder and empty G﹠W and the salt solution one or more are directly contacted, so that passivation and the frangible powder of production are kept described oxygen concentration simultaneously and are lower than about 1800ppm.
A further object of the present invention provides a kind of production and has the titanium particle of the passivation that is less than the about 900 parts/oxygen concentration of 1,000,000 parts (ppm) or the method for titanium alloy particle; comprise and the halide vapor of the metal ingredient of the halide vapor of titanium or described alloy is incorporated in the logistics of the liquid base metal that forms conversion zone or liquid base earth metal or their mixture with the velocity of sound or higher speed; wherein; described halide is reduced by the described liquid metals that exists with abundant excessive stoichiometric proportion; so that reduce Ti powder or the Ti alloy powder that described halide obtains by described liquid metals is frangible; by excessive liquid metals and described Ti powder or described Ti alloy powder being separated at least partially in filtration under the vacuum and distillation; described Ti powder or described Ti alloy powder at high temperature kept to be enough to make in vacuum or inert atmosphere or its combination form described particles of powder and grow into a period of time of measuring the average diameter of being calculated by the BET surface area greater than about 1 micron; described Ti powder or Ti alloy powder are cooled to about 70 ℃ or lower temperature; and with the cooling Ti powder or Ti alloy powder contact with air; so that the described particle of passivation; the described oxygen concentration of keeping described powder simultaneously is lower than about 900ppm; and wash the powder of described passivation, so that produce frangible metal dust and remove other product.
Last purpose of the present invention provides the system of a kind of production passivation and frangible metallic particles, comprises the storage container of the halid supply that fills the metal or alloy that will produce; Fill the storage container of the supply of reducing metal; Set up the pump installation of the flow stream of liquid reducing metal; Comprise be used for halide vapor be incorporated into the liquid reducing metal that forms conversion zone flow stream nozzle and produce metal dust and the device of the product of halide salts, wherein said liquid metals exists with the excessive stoichiometric proportion that the temperature that is enough to keep the described product that breaks away from described conversion zone is lower than the sintering temperature of described metal dust; Separation equipment, it comprises: one or more filters, distilling apparatus, be used for described product and heat and/or cold gas contact to heat and/or cool off described product and described reducing metal and described metal dust separate and make the germination that forms described metal dust simultaneously so that have device greater than about 1 micron average diameter by BET surface area measurement calculating; Contact with metal dust and air that will cooling and/or water and/or salt solution so that frangible metal dust of passivation and production and device that described salt and described frangible metal dust are separated.
The present invention includes some new feature and fully description hereinafter, illustrate and special combination with the pointed part of claims with accompanying drawing, should be appreciated that, can make detailed various variations, and not depart from aim of the present invention or sacrifice any advantage of the present invention.
The accompanying drawing summary
For helping to understand purpose of the present invention, for example understand the preferred embodiments of the invention in the accompanying drawings, when considering in conjunction with following description, from the inspection of this preferred embodiment, the present invention, its structure and operation and its many advantages will should be readily appreciated that and learn.
Fig. 1-the 4th is in the diagram that is used for producing the each several part of the system that uses in the method for frangible passive metal powder and equipment described herein.
Detailed Description Of The Invention
With reference to the accompanying drawings, disclose system 10, from system 10, produced frangible and metal dust passivation.Metal and the alloy thereof that can make according to described system hereinafter are Ti, Al, Sn, Sb, Be, B, Ta, Zr, V, Nb, Mo, Ga, U, Re, Si or their alloy, and all before disclosed in reference of above institute and the patent incorporated into.System 10 comprises sodium supply system 11, chloride supply system 12, reactor 15, Distallation systm 16, growing system 17, cooling system 18, washing system 19 and drying system 21.
Although this paper is described with regard to chloride and sodium reduction metal,, obviously can use any halide and can use various alkali metal and alkaline-earth metal or mixture.Commercial, in the reduction of for example titanium, sodium and magnesium are prevailing reducing metals.In Russia, used calcium as the reducing metal.Although hereinafter described system specifically at chloride and sodium, desires to make the present invention not limited especially.
Such as among the figure use, PT is a pressure transmitter, PSV is a pressure-reducing valve, PSE is a safety plate, PSH is a pressure switch, FT is a flow transmitter, and CV is a flow control valve.The engineering sensor of these standards and controller will not described in addition.
Especially as shown in figs. 1 and 3, be incorporated into a series of filters 49 and heat exchanger 50 by pump 47 and cooling fan 48, enter into reactor 15 from the sodium that replenishes loop 45,46.The head tank 52 that is used for sodium also is included in system 10, and all is connected with pipeline in replenishing loop 45,46.At last, sodium supply system 11 comprises the condenser escaper 53 and 54 that is connected with the product of leaving reactor 15, as shown in Figure 3, and has condenser 55, cooling fan 57 and the condensate 58 that connects by sodium condenser vapor header 56.The condenser vavuum pump 61 and the condensate reflux pump 62 that are connected in condensate backflow 63 and/or the condensate backflow 64 are connected with storage tank 35, and all will be as hereinafter explaining, so that finish sodium loop.
With reference to figure 2, it discloses halide or chloride supply system 12 in more detail, and comprises titanium tetrachloride raw material and the titanium tetrachloride day tank 70 that is connected with the bigger titanium tetrachloride supply that does not illustrate.Jars 70 are connected with a pair of titanium tetrachloride boilers 73 and 74 by a series of pump 71, and each boiler has its oneself heater 76.Point out that as described above the description of this paper promptly in two modules shown in the patent of incorporating into, therefore, has two boilers as described at two reactor 15 systems, two reactors are respectively with one.It will be apparent to those skilled in the art that if more reactor is arranged,, will be useful on the boiler of each alloying component so if more boiler is then arranged and will produce alloy.
For alloy, for example mainly form and be described to the most frequently used 6/4 titanium alloy of titanium 5 alloys of ASTMB265 class 5 by the vanadium of 6% aluminium and 4%, the vanadium chloride boilers 83 and the vanadium chloride boilers 84 that are connected to vanadium chloride day tank 80 by pump 81 are provided.Vanadium chloride boilers 83 and 84 each provide its oneself heater 86 and be connected on the reactor 15 by various pipeline collectors, as hereinafter stating.Similarly, provide aluminum chloride day tank 90, and be connected on aluminium chloride boiler 93 and 94 by a series of valves 91.Boiler 93 and 94 each provide heater 96 and unloading jars 97 and platform scale 98 so that the quantity of the aluminium chloride that weighing is used in the production of alloy.The difference that is used between the system of aluminium chloride and vanadium chloride is that aluminium chloride at room temperature is solid, and can be used as solid and be sent to boiler 93 by valve 91 from day tank 90.Use platform scale 98 to guarantee the correct quantity of aluminium chloride, thereafter it is provided on boiler 93 and 94.As noted, the various halide of described alloying component or chloride from the boiler feed to the common pipe or in the collector, enter into continuous reactor 15 with the liquid reducing metal that therefrom flows through (such as but not limited to liquid sodium or liquid magnesium) by pipe, valve etc. then.
With reference now to Fig. 3,, described liquid reducing metal for example sodium is incorporated into the reactor 15 from heat exchanger 50 as logistics, and metal chloride is incorporated into the speed of velocity of sound at least in the logistics of liquid reducing metal preventing that this liquid metals is back in this halide supply, and in reactor, produce the product of metal dust (it can be an alloy), salt and existing excessive reducing metal.Such as understanding, for halid amount, the excessive reducing metal of stoichiometric proportion will help when steam halide being injected or be incorporated into the logistics of motlten metal, and the homeostatic reaction temperature maintenance that will produce in the short distance downstream of conversion zone is at setting.Definite temperature is unknown in conversion zone, but several inches downstream, make steady temperature measured and all be controlled in anywhere about 800 ℃ to about 300 ℃ or lower, for sodium and titanium tetrachloride.Excessive stoichiometric proportion preferably is used for producing between 10 times to 100 times of stoichiometric proportion of metal dust at needs, and metal is crossed surplus, and the temperature of stable state is just low more.Operation and use between the extra excessive liquid reducing metal balance on the engineering is arranged for keeping lower steady temperature under higher temperature, all these is within the ordinary skill of this area.If use magnesium rather than sodium, then the fusion temperature owing to magnesium needs higher running temperature.
From collecting pipe 115, the material that breaks away from most of sodium or liquid reducing metal now is introduced in the distillation auger conveyor 120, this auger conveyor provides outlet 125 or collecting pipe and two valves 121 and 123, so that will distill auger conveyor is connected on the vacuum system 122, and will distill conveyer and heat treatment calcinatory 130 is kept apart, will explain as institute.
When material moved with the form of spiral by distillation conveyer 120, the sodium of discharging from distillation conveyer 120 was transported to condenser escaper 54 by pipeline, and turned back to sodium supply 11.Because distillation auger conveyor 120 is connected to condenser 55, cooling fan 54 and condensate 58 by collector 56, removes this reducing metal steam in distillation in the auger conveyor, and as described earlierly turn back to sodium supply system 11 once more by pump 62.
Be clear that in this system, most of excessive sodium remove, and turn back to the sodium supply system from product, the sodium that in the production of salt, uses that only stays the sodium carried secretly and lost.Can or can be not with the salt electrolytic separation, so that recirculation sodium, this depends on economic benefit.
Especially in Fig. 3 illustrated growth station 17, it comprise by valve 121 and 123 be connected to the distillation conveyer 120 outlet on going barrel calcinatory 130.As known in the art, calcinatory 130 rotation, by engineering philosophy after the predetermined time of staying of institute, material wherein is sent in the cooling and passivation system 18 that comprises the auger conveyor with outlet 136 by exporting 131.Done as other heat exchanger of great majority in goal systems 10, cooling conveyer 135 uses oil coolings but, because have liquid sodium or liquid magnesium, the two all is explosive reaction in the presence of water.Because the material in calcinatory 130 is under the high temperature, so should there be protective atmosphere such as the preferred argon gas of inert gas.
Cooling and passivation conveyor 135 will be wherein material temperature drop to 100 ℃ of also preferably about 80 ℃ or lower temperature of being less than from preferably exceeding 700 ℃ and preferred about 750 ℃ temperature in calcinatory 130 slightly in outlet 136.In this process in this, except the sodium of in particle, being carried secretly, nearly all sodium all is removed, remaining product (it is the mixture of salt and metal dust) is transported to material cake silo converter valve 139, and therefore arrive material cake storage silo 151 and 152 by outlet 141 and 142, as shown in Figure 4.The material cake accumulates in storage silo, opens so that by converter 156 or 157 material is transported to material cake slurry jar 160 until rotary valve 153 and 154.Wherein, will expect the cheese pulping by the water supply 161 that is connected on jar (forming slurry in this jar), this slurry is introduced in the vacuum belt filter 170 that is connected on the vacuum system 178 then.To be used for being fed to the cleaning water pot 165 from supplying 161 (it is by filter 162 and various optional deionization towers 163) at slurry jar 160 water that form slurry.Flow to the exit portion of material cake slurry jar 160 and vacuum belt filter 170 from the clean water of jar 165.Vacuum belt filter 170 is comprised in the shell 171, and has the nozzle that vertically separates, and it also is connected on intermediate salt wash tank 167 and the concentrated salt wash tank 168 by suitable pump 173.Water of discharging by powder on conveyer 170 or salt solution turn back to suitable jar 168 by pump 174 or turn back to unshowned salt solution device for transferring or salt solution discharge system.Go out as shown, the powder on conveyer belt filter 170 contacts with salt solution at first, and the water of low salt concn contacts with having more thereafter, until at last with can be heated contact from the water of the cleaning of jar 165.
Material cake silo 151,152 is in and is lower than 100 ℃, preferred 80 ℃ or lower and 40 ℃-80 ℃ temperature most preferably.Be connected to washing dust outlet skewed slot 177 on the vacuum belt filter 170 carry be passivated and water and/or the washed powder of salt solution to inertia turbo dryer 180.Fines collection pressure filter 179 is connected with the powder conveyor shell 171 of approaching outlet skewed slot 177, so that collect from the fine powder of conveyer 170.
Inertia turbo dryer 180 is connected to condenser 181, condenser fan 182 and condensate and returns on the pump 183, in view of the above from passivation and be to remove steam the frangible powder now.According to the economy instruction, steam is returned or removes.Therefore as discussed previously, inertia turbo dryer 180 is in such as under argon gas or the protection of nitrogen gas atmosphere, has connected argon gas inlet or nitrogen inlet 185 to protect powder after passivation, and it is at high temperature simultaneously.
At last, product outlet 190 is connected on a series of drum 192 from turbo dryer 180, this drum 192 can be placed on outlet 190 times, and design is filled with a certain speed according to system.
In the operation, be exemplary, and do not limit the present invention, the sodium storage tank preferably is maintained under the high temperature, so that sodium therein is liquid.The fusing point of sodium is about 98 ℃, so sodium storage tank 35 and 40 maintains about 105 ℃, and sodium head tank 52 maintains about 125 ℃-300 ℃, preferably about 125 ℃.Chen Shu definite temperature and/or pressure are considered through engineering hereinafter, so scope is exemplary, are not intended to limit the present invention.
Titanium tetrachloride boilers 73,74 maintains about 220 ℃, causes the about 500kPa of pressure, but can be under the pressure of about 800kPa at the most.Under the pressure that vanadium chloride boilers 83,84 and aluminium chloride boiler 93,94 maintain greater than titanium tetrachloride boilers, because have to greater than the pressure of titanium chloride boiler, turn back in the alloying component boiler to prevent titanium chloride from the residing pressure of the steam of each alloying component boiler.For example, if titanium tetrachloride boilers 73,74 is under the 500kPa, VCl so
4Boiler, AlC
4Boiler maintains under about 800kPa.
Cooling in system 10 and heating are to be undertaken by coil pipe in the mode of heat transmission, wherein, for security consideration, use oil as heat transfer medium.Silo 151 and 152 operation at ambient temperature in air usually, and mainly remain on powder by under the temperature of introducing from conveyer 135, promptly in the scope between about 40 ℃ to 80 ℃.After air passivation, wash or do not have air passivation directly to wash, washing is carried out at ambient temperature, with last washing agent, it is the water from fresh water tank 165, can be heated to help dissolving salt and to help heating the powder that enters into inertia turbo dryer 180.
Usually, the powder that enters into turbo dryer 180 is in from the ambient water tap temperature in about 70 ℃ temperature range.
At last, the powder that leaves inertia turbo dryer 180 at outlet 190 places preferably is under about 60 ℃ temperature, powder not too has reactivity under this temperature, should be appreciated that, under higher temperature, powder has more reactivity than more under the low temperature, particularly the powder in the 1-10 micrometer range, this size is after the formation particles of powder is left calcinatory 130, measures determined preferred particle size by BET.As what understand by the patent of being incorporated into, the metallic particles that comes out from reactor 15 have usually by the BET surface area measure calculated from about 0.1 micron to about 1 micron average diameter.Yet these particles are too little for many powder that are used for metallurgical applications, and therefore, it needs growth, and this is the purpose of calcinatory 130.At high temperature cause germination so that some is grown in the filter 115 takes place although powder kept, but distilling conveyer 120 and be sent to thereafter in the process of hot calcinatory 130, most germination takes place in calcinatory 130, for chemical pure titanium or titanium 6/4 alloy, it is about 6 hours with the time of staying that temperature is about 750 ℃.Can be at various speeds of production and equipment size design system 10, as the skilled personnel to understand, operating condition will change.Although argon gas is pointed out as preferred inert gas, if temperature maintenance is enough low, can be used nitrogen and neon or other inert gas, and not have influence on powder nocuously.Although the design does not here have air blast, expect that cake silo 151 and 152 may need air blast to circulate extra air with the material cake of passivation by cooling and passivation conveyor 135 productions.In addition, by cooled powder and inert gas and the mixture of about 20% oxygen are at the most contacted with counter-current relationship passivation can take place, but previous described method is preferred.
Should be appreciated that, enter into the cooling and the material of passivation conveyor 135 and be in protective atmosphere, but it exports 136 by conveyer and leaving under low temperature more, and have the air of some existence from heat treatment calcinatory 130.The alternative approach that is used for passivation is that powder is introduced directly into washing and drying system 19, rather than at first uses air passivation and wash then.Preferably at first use air passivation after passivation, to wash then, but for cost and economic reasons, it may be preferred washing immediately after powder comes out from cooling passivation conveyor 135.Although air passivation is washed the oxygen concentration that provides lower then, for example for the 900ppm of chemical pure titanium, it is equivalent to the titanium of ASTM B265 grade 1, but does not have the direct water washing (water and/or salt solution) of air passivation that the oxygen concentration of about 1800ppm is provided.The final use that depends on powder does not always need lower oxygen content.Therefore can adopt water and/or the direct passivation of salt solution or direct passivation of air or their combination, described combination is that air passivation is wherein to use the washing of some passivation then.
Although shown specially and described the present invention with reference to the preferred embodiment here, it should be appreciated by those skilled in the art, some variations be can make in form and details, and aim of the present invention and scope do not departed from.
Claims (47)
1. method of producing the passive metal powder, comprise the metal halide steam is incorporated in the logistics of the liquid base metal that forms conversion zone or liquid base earth metal or their mixture, wherein, described halide vapor is reduced by the described liquid metals that exists with abundant excessive stoichiometric proportion, so that reduce the metal dust that described halide vapor obtains by described liquid metals is frangible, from product, separate the most of at least of described excessive liquid metals, described metal dust growth is had greater than about 1 micron until the particle that forms described metal dust measure the average diameter of being calculated by the BET surface area;
Cool off described metal dust; And
The metal dust of cooling directly contact with air and/or water and/or salt solution, so that the passivation metal dust frangible with production.
2. the process of claim 1 wherein that described metal is the alloy of one or more or they among Ti, Al, Sn, Sb, Be, B, Ta, Zr, V, Nb, Mo, Ga, U, Re, the Si.
3. the method for claim 2, wherein said separation are included in distills under the vacuum and at high temperature keep described powder under vacuum or under inert atmosphere, is about 1 micron until the average particle size particle size of being measured the described metal dust that is calculated by the BET surface area.
4. the method for claim 2, wherein said separation comprise and contact with inert purge gas and at high temperature keep described powder, are at least about 1 micron until the average particle size particle size of being measured the described metal dust that is calculated by the BET surface area.
5. the method for claim 2, wherein said metal dust moves in most at least growth and cooling period.
6. the method for claim 2, wherein said separation comprise filtration and described powder after filtration, wash before great majority move.
7. the process of claim 1 wherein and when described metal dust is carried by the filter band, wash described metal dust by contacting with salt solution and/or water.
8. the process of claim 1 wherein and partly wash described metal dust by the contact between the salt solution of described metal dust and variable concentrations.
9. the process of claim 1 wherein greater than described reduction takes place under the atmospheric pressure.
10. the process of claim 1 wherein that described metal dust is that alloy and described halide are chlorides.
11. the method for claim 7, wherein dry described washed metal dust under described inert atmosphere.
12. method of producing the passive metal powder, comprise that halide vapor with described metal is incorporated in the logistics of the liquid sodium metal that forms conversion zone or liquid magnesium metal, wherein, by reduce described chloride at the described liquid sodium metal that exists with abundant excessive stoichiometric proportion or liquid magnesium metal, so that the described metal dust that forms by described liquid sodium metal or the described halide vapor of described liquid magnesium metallic reducing is frangible;
Product and most at least described excessive sodium metal or magnesium metal are separated;
Described metal dust is at high temperature kept a period of time that is enough to make described powder growth, have greater than about 1 micron until the described particles of powder of formation and measure the average diameter of being calculated, described metal dust is cooled to be lower than about 100 ℃ by the BET surface area; And
The metal dust of described cooling and air and/or water and/or salt solution are contacted, so that passivation and produce frangible metal dust.
13. the method for claim 12, wherein said metal dust are transition metal or its alloy.
14. the method for claim 13, wherein said transition metal are Ti or its alloy.
15. described reaction is wherein taking place from about 1 in the method for claim 14 under about 3 atmospheric pressure.
16. the method for claim 12 is wherein separated most described liquid sodium metal or described liquid magnesium metal and described product and is comprised and filtering and/or distillation.
17. the method for claim 12 wherein maintains described metal dust and is not less than under about 700 ℃ temperature, is used for the growth of the described powder particle of at least a portion.
18. the method for claim 17 wherein before passivation, is cooled to be not more than about 80 ℃ with described powder from high temperature on conveyer.
19. the method for claim 18, wherein said metal dust is at first used air passivation, uses salt solution and/or water washing then.
20. the method for claim 19, wherein most passivation and washing are taking place when described metal dust is on described conveyer.
21. the method for claim 20, at least a portion size growth of wherein said powder occurs in the going barrel.
22. the method for claim 19, wherein said frangible metal dust is dry in inert atmosphere after the washing.
23. a production has the titanium powder of the passivation that is less than the about 1800 parts/oxygen concentration of 1,000,000 parts (ppm) or the method for titanium alloy powder, comprise that halide vapor with the metal ingredient of the halide vapor of titanium or described alloy is incorporated in the logistics of the liquid base metal that forms conversion zone or liquid base earth metal or their mixture, wherein, described halide is reduced by the described liquid metals that exists with abundant excessive stoichiometric proportion, is frangible so that reduce Ti powder or the Ti alloy powder that described halide obtains by described liquid metals;
Described Ti powder or described Ti alloy powder product are separated with most at least described excessive liquid metals;
Described Ti powder or described Ti alloy powder at high temperature kept is enough to make the germination that forms described Ti powder or Ti alloy powder to a period of time greater than about 1 micron average diameter of being calculated by the measurement of BET surface area, cools off described Ti powder or described Ti alloy powder; And
In the Ti powder of cooling or Ti alloy powder and empty G﹠W and the salt solution one or more are directly contacted, so that passivation and the frangible powder of production are kept described oxygen concentration simultaneously and be lower than about 1800ppm.
24. the method for claim 23, wherein said water before washing by deionization.
25. the method for claim 23, wherein said water before washing by deoxidation.
26. the method for claim 23, wherein said passivation mainly are to carry out and be less than about 900ppm at the Ti of described passivation or the oxygen concentration in the Ti alloy with air.
27. the method for claim 26 is with salt solution and/or water washing after the wherein said passivation.
28. the method for claim 23 is wherein at high temperature kept described Ti powder or Ti alloy powder to be enough to make forming a period of time that described particles of powder grows into the about 10 microns average diameter of being calculated by the measurement of BET surface area of about 1-.
29. the method for claim 23 wherein during most at least growth time, remains on described Ti powder or described Ti alloy powder at least about under 700 ℃ the high temperature.
30. the method for claim 23 wherein before the described powder of passivation, is cooled to described powder under about 80 ℃ or the lower temperature.
31. comprising by described metal dust, the method for claim 23, wherein said product carry until the salt that is washed.
32. the method for claim 23, wherein said halide vapor comprises chloride, and described liquid metals comprises that the temperature of the liquid metals in sodium or magnesium and described conversion zone downstream is higher than about 200 ℃ of the fusing point of described reducing metal.
33. the method for claim 32, wherein said method great majority are continuous.
34. the method for claim 33, wherein when described reducing metal was sodium, the described small part that is separated to was undertaken by be lower than the distillation of implementing under about 550 ℃ temperature under vacuum.
35. the method for claim 33, the wherein said small part that is separated to is undertaken by the inert gas of heat being sent to contact with at least some described product, to remove the reducing metal that some are carried secretly.
36. the method for claim 33, wherein said liquid metals is a sodium.
37. the method for claim 36, wherein in great majority growth and cooling procedure, described Ti metal or Ti alloy are to move continuously.
38. the method for claim 37, wherein said liquid sodium are lower than under about 400 ℃ temperature being in before the introducing of described halide vapor to be lower than under about 300 ℃ temperature and to be maintained at the described liquid sodium in the downstream of described conversion zone, separate until beginning.
39. a production has the titanium particle of the passivation that is less than the about 900 parts/oxygen concentration of 1,000,000 parts (ppm) or the method for titanium alloy particle, comprise and the halide vapor of the metal ingredient of the halide vapor of titanium or described alloy is incorporated in the logistics of the liquid base metal that forms conversion zone or liquid base earth metal or their mixture with the velocity of sound or higher speed, wherein, described halide is reduced by the described liquid metals that exists with abundant excessive stoichiometric proportion, is frangible so that reduce Ti powder or the Ti alloy powder that described halide obtains by described liquid metals;
By excessive liquid metals and described Ti powder or described Ti alloy powder being separated at least partially in filtration under the vacuum and distillation;
Described Ti powder or described Ti alloy powder at high temperature kept to be enough to make forming described particles of powder and grow into a period of time of measuring the average diameter of being calculated by the BET surface area greater than about 1 micron in vacuum or inert atmosphere or its combination,
Described Ti powder or Ti alloy powder are cooled to about 80 ℃ or lower temperature, and with the cooling Ti powder or Ti alloy powder contact with air, so that the described particle of passivation, the described oxygen concentration of keeping described powder simultaneously is lower than about 900ppm, and wash the powder of described passivation, so that produce frangible metal dust and remove other product.
40. the method for claim 39 wherein is in the suds and uses the salt solution of deionized water and/or deoxygenated water and variable concentrations.
41. the method for claim 40, wherein said liquid reducing metal are with about 10 times of sodium that exist to about 100 times stoichiometric quantity.
42. the method for claim 41, wherein liquid sodium is lower than under about 400 ℃ temperature being in before the introducing of described halide vapor to be lower than under about 300 ℃ temperature and to be maintained at the described liquid sodium in the downstream of described conversion zone, separates until beginning.
43. the method for claim 42, wherein under inert atmosphere, the heating under at least about 700 ℃ high temperature of described powder is enough to make form described particles of powder to measure the average diameter of being calculated by the BET surface area be about 10 microns a period of time of about 1-.
44. the method for claim 43 wherein maintains described powder in the inert atmosphere in most of cooling procedures, until the beginning passivation.
45. the titanium powder of producing according to the method for claim 44.
46. the titanium alloy powder of the V that comprises about 6% Al and about 4% that produces according to the method for claim 44.
47. a system that produces passivation and frangible metallic particles comprises the storage container of the halid supply that fills the metal or alloy that will produce, fills the storage container of the supply of reducing metal;
Set up the pump installation of the flow stream of liquid reducing metal, comprise be used for halide vapor be incorporated into the liquid reducing metal that forms conversion zone flow stream nozzle and produce metal dust and the device of the product of halide salts;
Wherein said liquid metals is lower than with the temperature that is enough to keep the described product that breaks away from described conversion zone under the excessive stoichiometric proportion of sintering temperature of described metal dust and exists;
Separation equipment, comprise one or more: filter, distilling apparatus, be used for described product and heat and/or cold gas contact to heat and/or cool off described product and described reducing metal and described metal dust separate and make the germination that forms described metal dust simultaneously so that have device greater than about 1 micron average diameter by BET surface area measurement calculating; And
Metal dust and the air of cooling and/or water and/or salt solution contact so that frangible metal dust of passivation and production and device that described salt and described frangible metal dust are separated.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2006/048828 WO2008079115A1 (en) | 2006-12-22 | 2006-12-22 | Direct passivation of metal powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101568398A true CN101568398A (en) | 2009-10-28 |
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ID=38267707
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800567580A Pending CN101568398A (en) | 2006-12-22 | 2006-12-22 | Direct passivation of metal powder |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2104583A1 (en) |
| CN (1) | CN101568398A (en) |
| AU (1) | AU2006352435A1 (en) |
| WO (1) | WO2008079115A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103635274A (en) * | 2011-07-01 | 2014-03-12 | 通用电气公司 | Continuous process for the production of titanium alloy powders |
| CN108602128A (en) * | 2016-01-13 | 2018-09-28 | 株式会社丰山控股 | The method and its Preparation equipment of the copper metal nanometer powder with uniform oxygen passivation layer are prepared by using hot plasma |
| CN111112628A (en) * | 2020-01-15 | 2020-05-08 | 北京科技大学 | Method for preparing fine-grained low-oxygen titanium and titanium alloy powder by using cutting waste |
| WO2021168978A1 (en) * | 2020-02-24 | 2021-09-02 | 北京科技大学 | Method for preparing oxygen-free passivation titanium and titanium alloy powder product by gas-solid fluidization |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070017319A1 (en) | 2005-07-21 | 2007-01-25 | International Titanium Powder, Llc. | Titanium alloy |
| US20070079908A1 (en) | 2005-10-06 | 2007-04-12 | International Titanium Powder, Llc | Titanium boride |
| US7753989B2 (en) | 2006-12-22 | 2010-07-13 | Cristal Us, Inc. | Direct passivation of metal powder |
| US9127333B2 (en) | 2007-04-25 | 2015-09-08 | Lance Jacobsen | Liquid injection of VCL4 into superheated TiCL4 for the production of Ti-V alloy powder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6409797B2 (en) * | 1994-08-01 | 2002-06-25 | International Titanium Powder Llc | Method of making metals and other elements from the halide vapor of the metal |
| WO2005019485A1 (en) * | 2003-08-22 | 2005-03-03 | International Titanium Powder, Llc. | Indexing separation system |
-
2006
- 2006-12-22 AU AU2006352435A patent/AU2006352435A1/en not_active Abandoned
- 2006-12-22 CN CNA2006800567580A patent/CN101568398A/en active Pending
- 2006-12-22 WO PCT/US2006/048828 patent/WO2008079115A1/en active Application Filing
- 2006-12-22 EP EP06847931A patent/EP2104583A1/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103635274A (en) * | 2011-07-01 | 2014-03-12 | 通用电气公司 | Continuous process for the production of titanium alloy powders |
| CN108602128A (en) * | 2016-01-13 | 2018-09-28 | 株式会社丰山控股 | The method and its Preparation equipment of the copper metal nanometer powder with uniform oxygen passivation layer are prepared by using hot plasma |
| CN108602128B (en) * | 2016-01-13 | 2021-07-09 | 株式会社丰山控股 | Method for preparing copper metal nanopowder with uniform oxygen passivation layer by using thermal plasma and apparatus for preparing the same |
| CN111112628A (en) * | 2020-01-15 | 2020-05-08 | 北京科技大学 | Method for preparing fine-grained low-oxygen titanium and titanium alloy powder by using cutting waste |
| WO2021168978A1 (en) * | 2020-02-24 | 2021-09-02 | 北京科技大学 | Method for preparing oxygen-free passivation titanium and titanium alloy powder product by gas-solid fluidization |
| US11612936B2 (en) | 2020-02-24 | 2023-03-28 | University Of Science And Technology Beijing | Method for preparing oxygen-free passivated titanium or titanium-alloy powder product by means of gas-solid fluidization |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2006352435A1 (en) | 2008-07-03 |
| WO2008079115A1 (en) | 2008-07-03 |
| EP2104583A1 (en) | 2009-09-30 |
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