EP2247398A1 - Poudre métallique ou poudre d'alliage stabilisée et procédé et cuve de réaction pour la produire - Google Patents

Poudre métallique ou poudre d'alliage stabilisée et procédé et cuve de réaction pour la produire

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Publication number
EP2247398A1
EP2247398A1 EP09703271A EP09703271A EP2247398A1 EP 2247398 A1 EP2247398 A1 EP 2247398A1 EP 09703271 A EP09703271 A EP 09703271A EP 09703271 A EP09703271 A EP 09703271A EP 2247398 A1 EP2247398 A1 EP 2247398A1
Authority
EP
European Patent Office
Prior art keywords
metal
powder
reduction
alloy powder
metal powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09703271A
Other languages
German (de)
English (en)
Other versions
EP2247398B1 (fr
Inventor
Ulrich Gerhard Baudis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TRADIUM GMBH
Original Assignee
Tradium GmbH
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Filing date
Publication date
Application filed by Tradium GmbH filed Critical Tradium GmbH
Priority to PL11180240T priority Critical patent/PL2394762T3/pl
Priority to EP11180240.1A priority patent/EP2394762B1/fr
Publication of EP2247398A1 publication Critical patent/EP2247398A1/fr
Application granted granted Critical
Publication of EP2247398B1 publication Critical patent/EP2247398B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B19/00—Combinations of different kinds of furnaces that are not all covered by any single one of main groups F27B1/00 - F27B17/00
    • F27B19/02—Combinations of different kinds of furnaces that are not all covered by any single one of main groups F27B1/00 - F27B17/00 combined in one structure
    • 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
    • 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
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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
    • 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
    • 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
    • C22B34/1277—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 other metals, e.g. Al, Si, Mn
    • 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
    • C22B34/14—Obtaining zirconium or hafnium
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D5/00—Supports, screens or the like for the charge within the furnace
    • F27D5/0068—Containers
    • F27D2005/0075—Pots, e.g. slag pots, ladles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the invention relates to the production of passivated, air-manageable finest metal powder of the elements zirconium, titanium and / or hafnium, having a mean particle size below 10 microns (measured by permeability methods such as the Blaine or Fisher method) by metallothermal reduction of their oxides by means of calcium and magnesium and a specially suitable reaction vessel consisting of retort crucible, retort lid and inner crucible, which enables the addition of phlegmatizing acting gases and / or solids before, during and / or after the reduction reaction.
  • hydrogen in an amount of at least 500 ppm and nitrogen in an amount of at least 1000 ppm are used as phlegmatizing additives, as phlegmatizing solid additives carbon, silicon, boron, nickel, chromium and aluminum in quantities of at least 2000 ppm.
  • the oxides can be individually reduced to produce pure metal powders. However, they may also be reduced in admixture with each other or in admixture with metal powders and / or oxides of the elements nickel, chromium and aluminum to produce alloys of titanium, zirconium and hafnium with these elements.
  • Metal-thermal reductions using calcium and magnesium as reducing agents are used to recover rare metals from their oxides when they are otherwise treated, for example, electrochemically from aqueous solutions, from molten salts or by reducing their oxides with carbon or with gases such as hydrogen or carbon monoxide are not or only in low purity to win.
  • a typical industrial example of this is the production of rare earth metals such as yttrium, cerium, lanthanum and others, and of the metal beryllium from their oxides or halides with magnesia.
  • the particle size of the metal powder to be obtained can be largely predetermined by the choice of the particle size of the corresponding metal oxide to be reduced [Petrikeev, et al., Tsvetnye Met., No. 8 (1991) 71-72].
  • EP 1 644 544 B1 also describes a process for the production of metal powders or metal hydride powders which mixes elements of Ti, Zr, Hf, V, Nb, Ta and Cr in which an oxide of these elements is mixed with a reducing agent and these
  • the mixture is heated in an oven under a hydrogen atmosphere until the reduction reaction begins, the reaction product is leached, and then washed and dried, the oxide employed having an average grain size of 0.5 to 20 ⁇ m, a specific surface area
  • pulverulent alloys for example by mixing zirconium oxide with titanium oxide, an alloy of Zr and Ti or of zirconium oxide with nickel and nickel oxide, an alloy of zirconium and nickel.
  • zirconium oxide with titanium oxide, an alloy of Zr and Ti or of zirconium oxide with nickel and nickel oxide, an alloy of zirconium and nickel.
  • the heat of the reduction depends on the oxides to be reduced, the reduction metal and possible side reactions. It can be calculated according to thermodynamic principles based on the free reaction enthalpy of the reactants and the products. The strongest reducing effect is generally metal calcium, followed by aluminum and magnesium.
  • the metal oxide of the reduction metal formed with the reduction should not form double oxides or other mixed oxides with the oxide to be reduced, because the yield is reduced by this parallel side reaction.
  • the metal oxide of the reduction metal formed with the reduction should not form double oxides or other mixed oxides with the oxide to be reduced, because the yield is reduced by this parallel side reaction.
  • the vapor pressure of the reducing metal at the expected reaction temperature usually 800 to 1400 0 C
  • the oxide formed in the reduction of the reducing metal must be soluble in water or aqueous acids in order to be able to remove it from the reaction mass by leaching after completion of the reaction.
  • the poor solubility of the oxides of silicon and aluminum as well as their tendency to form mixed oxides is the reason that these low-priced elements are often not used as a reducing agent.
  • Metal-thermal reduction reactions are generally self-contained. This term refers to reactions that are initiated by an initial ignition and then automatically continue to run without external energy input.
  • the initial ignition can be initiated chemically, electrically (by a filament or by induction) or simply by vigorously heating a portion of the metal / metal oxide mixture [DE PS 96317].
  • a gas-fired crucible furnace has the advantage that the retort is heated quickly. At a temperature of about 100 to 450 0 C, depending on the grain sizes and the type of feedstocks, sets an initial ignition fertil, which starts at a hot spot, which is usually laterally in the lower third of the crucible in which the is to be reacted mixture.
  • Resulting vapors and dusts must be extracted at the place of their formation.
  • the opening of the valve can be done manually, but also electromechanical or pneumatic, and it can be controlled for security reasons remotely, for example, under video observation.
  • As relief valves for the overpressure primarily sealless plug valves or ball valves with a large cross section are used.
  • Metal-thermal reductions continue to go on - when ignited - inexorably. Once initiated, the reaction can no longer be stopped using conventional processing techniques such as cooling or adding diluents.
  • Metallic titanium, zirconium, and hafnium, and alloys of these metals are only stable to air because they are surrounded by a dense, oxygen-impermeable, oxide or oxynitride envelope at room temperature, the so-called passive layer.
  • the passivation is also known from many other metals, such as aluminum, zinc and chromium. Passivation occurs automatically on most metals. By contact of the metal surface with the oxygen and nitrogen of the air, with moisture and in air Carbon dioxide builds up the protective passive film without any special action. This is not so with the metals Ti, Zr and Hf and their alloys, when they are in fine powder form and produced in a protective atmosphere under argon, helium or in vacuum.
  • the object of the present invention was therefore to provide a method and a reaction vessel for carrying out this process for the production of metal powders or alloy powders of the reactive metals zirconium, titanium or hafnium from the corresponding oxides or oxide mixtures, wherein the prepared reactive metal powders or alloy powders subsequently, For example, for the purpose of further processing, to be handled in the air.
  • the abovementioned object was achieved by a process for producing metal powder or alloy powder having a mean particle size of less than 10 ⁇ m, consisting of or containing at least one of the reactive metals zirconium, titanium or hafnium, by metallothermal reduction of oxides or halides of said reactive metals by means of a Dissolved reduction metal, wherein the metal powder or alloy powder
  • both the reduction and the phlegmatization are carried out in a single evacuable and gas-tight reaction vessel.
  • This procedure ren is carried out according to the invention in a suitable reaction vessel, which will be explained in more detail.
  • the process according to the invention and the reaction vessel allow the reduction reaction to be carried out under protective gases such as argon or helium or in vacuo in order to prevent uncontrolled access of air and moisture.
  • protective gases such as argon or helium or in vacuo in order to prevent uncontrolled access of air and moisture.
  • the construction further allows in particular the targeted addition of a measured amount of gases during and / or after the reduction reaction in order to specifically phlegmatize the metals or alloys formed and to influence their chemical behavior.
  • the construction further permits the reduction of the oxides or oxide mixtures under a reactive gas atmosphere, especially under hydrogen, when it is intended to produce hydrides of the metals Ti, Zr and Hf. It also allows the hydrogenation of alloys made by fusion metallurgy, e.g. an alloy of 70% Zr and 30% nickel or titanium sponge by heating and introducing hydrogen.
  • ammonia, methane, carbon monoxide, carbon dioxide and nitrogen may also be introduced into the retort to produce hydrides, subhydrides, carbides, nitrides, hydride-nitride mixtures or oxynitrides of the metals zirconium, titanium and hafnium.
  • the design incorporates a special flange and lid cooling design to prevent unwanted ingress of cooling water into the retort space.
  • a special spacer with support ring allows the retort to be inserted at different depths into the combustion chamber of the reduction furnace.
  • the reduction metal used is preferably calcium and / or magnesium. Calcium and magnesium can therefore be used individually or together. In principle, further additives, such as carbon, silicon or silicon oxide and other substances, can be added in order to influence the properties of the reactive metal powder produced during the reduction
  • a passivating gas preferably nitrogen and / or hydrogen is introduced.
  • At least 500 ppm of hydrogen and 1000 ppm of nitrogen should be present in the metal powders in order to avoid the above-mentioned reactions.
  • the amount of hydrogen should be at least 1000 ppm (0.1%), preferably 1000 to 2000 ppm, and nitrogen at least 2000 ppm (0.2%), preferably 2000 - 3000 ppm.
  • Nitrogen and hydrogen can also be introduced in the form of ammonia.
  • At least 2,000 ppm (0.2% by weight) and at most 30,000 ppm (3% by weight) of carbon, silicon, boron, nickel, chromium and / or aluminum can be introduced as passivating solids.
  • the passivating solid can also be introduced in the form of a fine oxide of the elements Ni, Cr, Al, Si and B with an average particle size of less than 20 microns and be reduced together with the metal oxide.
  • carbon can be introduced via the gas phase in the form of methane, carbon dioxide or carbon monoxide.
  • the passivating gases and solids can also be introduced together.
  • the ignitability of the phlegmatized metal powders or alloy powders can be further reduced by washing out submicroscopic particles of less than 0.2 ⁇ m grain size during leaching and / or washing.
  • a hypothetical idea of the inventor is the following: by the inclusion of the gases in the metal grid, the total energy level of the free electrons in the metal is lowered so far that the spontaneous reaction with oxygen under combustion or the reaction with water is omitted. In the subsequent wet-chemical preparation of the metal powders in water and acid, only the actual, oxidic passive layer on the particle surface is formed by a slow oxidation reaction with atmospheric oxygen or by slow reaction with water.
  • the effect of the incorporation of gases into the metal grid is to be exploited.
  • Such incorporation is advantageously achieved precisely in that the phlegmatizing compounds are added in particular already during the reduction reaction.
  • the degree of passivation is difficult to quantify, it can best be deduced from the ignition point of the metal powder in air.
  • various, sometimes even standardized, methods are available.
  • the following simple test arrangement is suitable for the metals Ti, Zr and Hf: in a copper or steel cylinder with a diameter and a height of 70 mm each, a hole of 15 mm diameter and 35 mm depth is drilled in the center.
  • thermocouple At a distance of 4 mm, a hole 5 mm thick, also 35 mm deep, is drilled to accommodate a thermocouple.
  • the block is preheated uniformly to about 140 - 150 0 C, then a quantity of 1 - 2 g of the metal powder to be tested is filled into the larger bore and it is heated further until ignition. This can be recognized optically (eg by video camera). By evaluating the time / temperature curve of the thermocouple you can determine the ignition point quite accurately. If the ignition points are below 150 0 C, one can not assume a safe passivation or phlegmatization. Metal powders with such low ignition points should be destroyed by burning in a safe place.
  • the firing time also indicates the degree of phlegmatization.
  • the method is described in Example 1. Information on this can also be found in measurements of the minimum electrical ignition energy, which is very difficult to determine. [Berger, B., Gyseler, J., Method for Testing the Sensitivity of Explosives to Electrostatic Discharge, Techn. Of Energetic Metals, 18 th Ann. Conf. of ICT, Düsseldorf 1987, pp. 55/1 to 55/14].
  • the phlegmatization of the metal powders of Ti, Zr and Hf and of alloy powders of these metals with Ni, Cr and Al occurs during and / or after the reduction in the evacuable and gas-tight retort by addition of a measured amount of hydrogen and / or nitrogen , Part of these gases can also be present in the retort from the very beginning.
  • the passivating gases can be introduced into the reaction vessel (the retort) upon reaching the peak temperature upon cooling of the reacted mass.
  • the elements Ni, Cr and Al have a dual function, they can not only serve for the production of alloys of Ti, Zr and Hf, but act in small amounts between 2000 ppm to 3% as phlegmatizing solid additives in the pure metals.
  • non-metallic additives such as carbon, silicon, boron or metallic additives such as iron, nickel, chromium, aluminum and others can influence the reactivity of zirconium, titanium and hafnium to water, air and oxidants.
  • Addition of silicon or boron generally slows down the burning rate only slightly, but can increase the ignition temperature.
  • a rather negative example is iron, additions of iron lead to spray sparks, lower the ignition temperature of the zirconium metal rather and usually increase the ignitability to friction.
  • Carbon can be introduced into the retort according to the invention by adding measured amounts of carbon dioxide or methane. It generally leads to phlegmatization. Other elements are better put in the form of their oxides or directly as a powder in elemental form the approach to.
  • the phlegmatization according to the invention of the metal powders of titanium, zirconium and hafnium or their alloy powder with gases can be realized on an industrial scale using a special reaction vessel (a retort).
  • This reaction vessel according to the invention for the production of phlegmatized metal powder or alloy powder having an average particle size of less than 10 microns, consisting of or containing at least one of the reactive metals zirconium, titanium or hafnium, by metallothermal reduction of oxides or halides of said reactive metals using a Reduction metal according to the described method is characterized in that the reaction vessel consists of a usable in a heatable reduction oven retort crucible with a coolable lid and an inner crucible, wherein in the coolable lid at least one nozzle for introducing a passivating acting gas or solid is incorporated and a flange is welded to the retort crucible for placing the retort lid on the underside a cooling for
  • the opening of tightly closed steel retorts after the implementation of a non-dangerous matter since there is often no information about the prevailing pressure.
  • Uncooled screw-retained retorts require a heat-resistant metallic or ceramic seal (copper, silver, or heat-resistant fibers) between the lid and the retort cup, which in most cases can only be used once.
  • large retorts are poorly sealed in this way, such seals only allow the use of small retorts on a kg scale or below.
  • the cooling is congruent under a ring on the flange extending seal and this cooling has no connection to the actual retort crucible.
  • any other cooling media can be used as an alternative to water.
  • organic heat transfer media such as heat transfer oils, preferably silicone oils, or even air can be used.
  • a suitable silicone oil can be obtained, for example, as Therminol® VP from Solutia GmbH.
  • the cooling media circulate in a common or in independent suitable cooling circuits.
  • the lid can have the following connections: a nozzle with a heat-resistant, seal-free ball valve or plug for discharging excess pressure, a nozzle for connecting a vacuum pump for evacuating the retort, and a nozzle for introducing inert gas, such as argon, out of a pipe , a nozzle for introducing reactive gases, such as H 2 or N 2 , from a pipe, a nozzle for receiving a safety valve, a nozzle for connection to a vacuum and pressure gauge and a nozzle for passing one or more thermocouples (Pt / RhPt) ,
  • a groove for receiving a sealing ring preferably made of Viton, unless provided on the retort tiegel, may be provided on the lid.
  • the water cooling can be configured, for example, as running on the lid annular channel.
  • the cooling of the retort lid has no connection to the nozzle and passages of the cover plate.
  • the cooling of the flange should have no connection to the retort crucible and the retort wall out.
  • FIG. 1 shows a reduction furnace with a reaction vessel for carrying out metal-thermal reductions in order to obtain the metals zirconium, titanium, hafnium and their alloys as well as other rare metals,
  • FIG. 2 shows a retort crucible
  • FIG. 3 shows a cooled retort cover
  • FIG. 4 shows a spacer
  • FIG. 5 shows an inner crucible.
  • the wall thickness is at least 10 mm, preferably 15 mm.
  • a flange 2 is welded with a material thickness of 30 mm and a ring width of 150 mm, on the underside of a cooling 3 is welded for cooling water.
  • the flange 2 is preferably also made of the heat-resistant steel 1 .4841 or a comparable steel.
  • the decisive design feature is that the cooling 3 is located precisely under a seal 4 which extends annularly on the flange 2 and this cooling 3 has no connection to the actual retort crucible 1.
  • the flange 2 allows the attachment of the lid 5, wherein between the cover 5 and the flange 2 of the sealing ring 4 made of Viton, Perbunan, Teflon or other common sealing material is used, which allows the gas and vacuum-tight connection between the lid and retort crucible.
  • the sealing ring 4 may optionally be inserted into a groove milled into the flange.
  • a support ring with a spacer 20 is screwed to the crucible flange 2, which makes it possible to use the retort at different depths in the furnace chamber and the combustion chamber 18 of the heatable reduction furnace 17.
  • Thieves- Heating of the reduction furnace 17 may preferably be effected by means of an electric heating 16.1 or alternatively a gas heating 16.2.
  • a spacer 20 with a support ring is provided between the flange 2 and the heatable reduction furnace 17.
  • the inner crucible 14 serves according to FIG. 5 for receiving the batch mixture 15, that is to say the mixture of the metal oxide and the reduction metal to be reduced.
  • the inner crucible 14 is made of structural steel, heat-resistant steel or stainless steel, preferably St37 or VA, in a thickness of 2 depending on the purity requirements to 5 mm, preferably 2 to 4 mm.
  • the inner crucible 14 keeps the reaction mass away from the actual retort, which serves only as "receiving vessel” for the duration of the reduction reaction
  • the inner crucible can be removed from the retort and optionally stored under protective gas in another vessel, eg a stainless steel drum until the preparation of the reduced mass contained in it, a protective tube 21 for receiving one or more thermocouples can be introduced into the batch mixture 15.
  • a particular inventive feature consists in the execution of the cooling of the cover 5 and flange 2 of the reduction retort.
  • Lid 5 and retort crucible 1 are gas-tight and vacuum-tight connected by a sealing ring 4 made of Viton, Perbunan, Teflon or other common sealing materials.
  • the seals 4 may be designed as a flat ring or as an O-ring.
  • the gaskets 4 must be cooled as they would be decomposed at the high reaction temperatures. The cooling takes place in this embodiment with water. It would be catastrophic if water entered the retort space through cracks or corrosion holes during the reduction reaction. This would lead to a violent evolution of hydrogen and an explosion of the retort.
  • the design of the cooling is therefore a very important feature of the reaction vessel.
  • the cooling 3 on the crucible flange is placed on the bottom of the flange 2 and has only one connection to the flange itself, but not to the retort wall. Thus, water can never penetrate into the retort from this area.
  • the cover 5, the cooling is designed so that it cools only the surface of the lid 5, but has no connection to the nozzle and bushings. The cooling water would have to penetrate through the solid lid 5 to get into the retort, which is very unlikely with a wall thickness of at least 30 mm heat resistant steel.
  • the cooling is shown in more detail as water cooling 6 in Fig. 3.
  • the retort crucible and retort lid are connected with a suitable number of screws and nuts 19.
  • the retort lid 5 and retort crucible 1 consisting of the retort lid 5 and Retortentiegel 1 can immediately with the reacted and phlegmatized mass after taking the inner crucible 14 for receiving another Inner tiegel can be used with a new approach. Thus, several retorts can be reacted one after the other in an oven.
  • An example of a metallothermal reduction using the above principles and the present invention is the recovery of zirconium in powder form by reduction of zirconium oxide with calcium for use in gettering (lamps, vacuum components) and military pyrotechnics, e.g. for the production of thermal batteries.
  • Zirconia with a mean grain size of 5 +/- 0.5 micron measured by the Blaine method or the Fisher Sub Sieve Sizer method, is mixed with calcium chips or granules of 0.5 to 5 mm size.
  • Calcium metal is added in the theoretically necessary stoichiometric amount.
  • a small amount, for example 2 to 10% by weight, of the theoretically necessary stoichiometric amount of magnesium chips of similar size to calcium is additionally added.
  • further additives for example carbon, silicon or silicon oxide and other substances can be added in order to influence the properties of the zirconium powder formed during the reduction.
  • the amount of gaseous additives is found to be in the range of 500 to about 5000 ppm in the later-isolated zirconium powder, and "impurity" in the case of solids of at least 2,000 to 3%, in the present example, a small amount of silica is incorporated.
  • the mixture of feedstocks takes place under argon in a Rhönrad mixer, a helical mixer or another comparable mixing device for solid substances.All feedstuffs must be kept awake dry by the addition of a small amount of second reduction metal (magnesium) is lowered the threshold of the initial ignition, so that the reaction mixture is easier to ignite than when using calcium alone. Since magnesium vaporizes earlier than calcium, the vaporization of magnesium removes heat from the reaction mass, thereby limiting the peak temperature of the reacting mass.
  • the starting materials are weighed in a drum mixer under Ar atmosphere, intimately mixed, transferred to an inner crucible and stored dry until used in the reduction of the invention under argon atmosphere.
  • the inner crucible with the mixture of feedstocks in the retort crucible according to the invention is used, the retort closed by placing the lid, the entire retort pumped out twice to a final pressure of less than 1 mbar to remove the air and any moisture, and with argon flooded.
  • a thermocouple is used to measure the temperature in the reaction space. It is connected to a pressure gauge, which displays both negative pressure to 0.1 mbar as overpressure to +1000 mbar.
  • Compounds are made to gas pressure bottles with argon, nitrogen and hydrogen.
  • the gas pressure bottles are equipped with fine pressure reducers, which are designed for a max. Print of 100 mbar are set.
  • the pressure cylinders for nitrogen and hydrogen are filled with measured quantities of these gases.
  • the protective gas argon must always be available in sufficient excess quantity. The reduction is then started by heating the retort in a gas-fired crucible furnace. About 45 minutes later, the metallothermal reduction reaction starts:
  • the reaction starts at a temperature of about. 100 - 140 0 C and it can be reached within 2 minutes 1 100 0 C. After exceeding the peak temperature, recognizable by the fall of the measured temperature in the reaction space by means of a thermocouple, the necessary for Phlegmatisie- tion or to adjust the burning and ignition properties of the zirconium metal powder gas quantities are introduced.
  • 50 liters of nitrogen and 130 liters of hydrogen from the connected compressed gas cylinders are added in the course of the cooling phase. This corresponds to an amount of 500 ppm of hydrogen and 2500 ppm of nitrogen in the resulting zirconium metal powder. The gases are rapidly absorbed by the zirconium metal during the cooling phase.
  • the inner crucible with the reaction mass is removed from the retort, the reaction mass broken out, crushed with a jaw crusher and leached in hydrochloric acid.
  • magnesium oxide and calcium oxide are converted to the corresponding chlorides and washed out.
  • What remains is a metal slurry of fine zirconium metal powder, whose Grain size about that of the zirconium oxide used, ie 5 +/- 1 microns measured by Blaine or Fisher. The metal powder is washed out, wet sieved ( ⁇ 45 microns) and carefully ( ⁇ 80 0 C) dried.
  • the metal powder can be processed safely in water and acid without reacting with water, and it can later be handled without spontaneous spontaneous combustion in air ,
  • the yield is 25-26 kg of a fine, gray zirconium metal powder.
  • the burning rate of the metal powder thus obtained is measured as follows: into a steel block of 60 cm in length, 1 cm in height and 4 cm in width, a rectangular gutter, which is 2 mm deep and 3 mm wide, is continuously milled.
  • the trough is filled with 15 g of the metal powder to be tested, the powder filling is ignited at one end and the time taken for the burning front to go through a marked distance of 500 mm distance is measured.
  • the burning time is 80 +/- 10 seconds / 50 cm.
  • the ignition temperature is 240 +/- 20 0 C.
  • the electrical energy to ignite is about 18 ⁇ j.
  • In the final product can be found due to a further hydrogen uptake in the aqueous workup, a total of 2000 ppm of hydrogen. Contaminants of the reduction metals are also found in the metal powders, but these quantities are generally low.
  • the found amount of 1800 ppm silicon, 2500 ppm nitrogen and 1000 ppm titanium corresponds quite well to the theoretical amount.
  • the retort is left in the reduction furnace after the reduction reaction with the reacted mass. Further heating from outside influences the grain size of the rare metal or its burning properties and chemical properties. By heating for several hours at about 900 0 C, a sintering effect can be achieved, which leads to a grain coarsening of the obtained zirconium metal. In the present example, by heating for 3-4 hours, the mean grain size of the zirconium metal can be increased from about 5 ⁇ m to 6-7 ⁇ m and the burning rate can be increased from about 75 s / 50 cm to 100 to 120 s / 50 cm. seed. The ignition point of the metal remains almost unchanged in this procedure and is at 250 0 C +/- 20 0 C.
  • Zirconium oxide (mean grain size 1, 5 / -0.25 / + 0.5 ⁇ m) 36.0 kg
  • Example (1) The starting materials are mixed as in Example (1), filled in the inner crucible and inserted into the retort. Unlike in Example (1), the retort is pumped out twice and then filled with 100 l of hydrogen, 50 l of nitrogen and the remainder of argon. After heating, the reduction reaction starts when reaching a temperature of 150 ° C +/- 20 0 C and reaches a maximum value of 960 to 1050 0 C according to the equation
  • the burning rate in a channel (see example (1) in air is 10 +/- 3 s / 50 cm.)
  • the mean particle size of the metal powder is 1.7 +/- 0.3 ⁇ m
  • Ignition point is 180 +/- 10 0 C.
  • the minimum electrical ignition energy was measured at about 2 ⁇ J.
  • the content of silicon corresponds approximately to the use and is 5900 ppm (theor. 6530 ppm).
  • the hydrogen content in the final product is 1400 ppm (theor. 900 ppm), due to a further hydrogen uptake in the acid leaching.
  • the nitrogen content in the final product is 4000 ppm (theoretical 5000 ppm).
  • the high degree of ignitability of the metal powder results from the high degree of fineness and the high sensitivity to electrostatic charging. These metal powders are generally not dried, but stored and traded in suspension under at least 30% by weight of water.
  • Zirconium oxide (average grain size 4.5 ⁇ m) 36.0 kg calcium granules 26.5 kg
  • the reaction is carried out as in Example (1), but the retort is filled after pumping not with argon, but with 100 l of nitrogen (99,995). By heating, the reaction is started, in this case it starts already at 80 to 100 0 C and reaches a peak value of about 1050 0 C.
  • reaction mass After complete cooling, the reaction mass is broken, but not crushed leached, but finely ground under Argon atmosphere and exclusion of moisture to a particle size below 150 microns.
  • Zr metal calcium oxide and magnesium oxide as well as excess magnesium and calcium are added to 12 kg nickel powder (mean particle size after Fsss 5 microns) (attention, Ni powders are carcinogenic) and mixed under argon atmosphere in a drum mixer.
  • the mass is then filled into the inner crucible, used in the retort according to the invention, evacuated and slowly heated under argon atmosphere, the oven temperature is limited to 860 0 C.
  • the oven temperature is reached after about 1 h, the internal temperature measured in the reaction mixture begins to rise after about 3 to 5 h, then it runs within 15 minutes of about 400 0 C to 880-900 ° C. The heating will be switched off as soon as the implementation starts.
  • the nickel oxide always contained in the nickel powder is reduced to Ni by the excess of reducing agent still contained in the Zr reducing mass, and at the same time, the Zr powder combines with the nickel to form a Zr-Ni alloy having a composition of 70 wt.% Zr and 30 wt.% nickel.
  • 200 l of hydrogen are added.
  • the reaction mass is allowed to cool overnight in the retort in a cooling rack under argon supply. After opening, the mass is broken up, crushed and leached in acid to wash out calcium and magnesium oxide. In this case, the leaching must be carried out in a strongly acetate-buffered hydrochloric acid, since the ZrNi alloy would be attacked by pure hydrochloric acid. The remaining as a suspension Zr / Ni alloy is wet sieved ( ⁇ 45 microns) and dried.
  • the obtained Zr-Ni alloy powder has a grain size of 4-6 ⁇ m measured according to Blaine or Fisher.
  • the yield is about 36 kg.
  • the one burning time is 200 +/- 30 s / 50 cm measured in the hearth described in Example (1).
  • the ignition point is 260 - 280 0 C, the hydrogen content at 0.2% (2000 ppm) compared to 500 ppm theoretically.
  • the nitrogen content was not determined, theoretically it is 1%. (10,000 ppm).
  • As electrical minimum ignition energy was determined about 100 ⁇ J.
  • the alloy powder is suitable for the production of delay igniters according to US specification MIL-Z-114108.
  • the zirconium metal powders produced in the described examples are phlegmatized according to the invention and are not spontaneously spontaneously flammable, ie manageable on access of air.
  • the aqueous workup itself also contributes to the passivation of the metal surface.
  • the latter also leads to the fact that Zr, Ti and Hf metal powders are surrounded by a thin oxide film and can thus be charged electrostatically.
  • Spontaneous ignition which is not based on "classical” spontaneous combustion but can be traced back to an electrostatic discharge, can then occur.Zr, Ti and hafnium metal powders must therefore always be handled in grounded, preferably metallic vessels and as far as possible When reprocessing the examples given in the invention, appropriate safety measures are to be taken and professional advice should be sought from trained safety experts.
  • thermocouple 11 Socket for connecting a vacuum and pressure gauge (manometer)

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Abstract

L'invention concerne un procédé et un dispositif pour produire une poudre métallique ou une poudre d'alliage présentant une granulométrie moyenne inférieure à 10 µm, composée de ou contenant au moins un métal hautement réactif parmi le zirconium, le titane ou l'hafnium, par réduction métallothermique d'oxydes ou d'halogénures desdits métaux hautement réactifs à l'aide d'un métal réducteur, la poudre métallique ou la poudre d'alliage étant stabilisée par addition d'un gaz ou d'un mélange gazeux à effet passivant pendant et/ou après la réduction des oxydes ou des halogénures et/ou par addition d'un solide à effet passivant avant la réduction des oxydes ou des halogénures, la réduction et la stabilisation étant toutes deux réalisées dans une seule cuve de réaction étanche aux gaz et pouvant être mise sous vide.
EP09703271.8A 2008-01-23 2009-01-08 Poudre métallique ou poudre d'alliage stabilisée et procédé et cuve de réaction pour la produire Not-in-force EP2247398B1 (fr)

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PL11180240T PL2394762T3 (pl) 2008-01-23 2009-01-08 Naczynie reakcyjne do wytwarzania flegmatyzowanych proszków metalowych lub proszków stopowych
EP11180240.1A EP2394762B1 (fr) 2008-01-23 2009-01-08 Une cuve de réaction pour la fabrication de la poudre métallique stabilisée ou de la poudre d'alliage stabilisée

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DE102008005781A DE102008005781A1 (de) 2008-01-23 2008-01-23 Phlegmatisierte Metallpulver oder Legierungspulver und Verfahren bzw. Reaktionsgefäß zu deren Herstellung
PCT/EP2009/050163 WO2009092631A1 (fr) 2008-01-23 2009-01-08 Poudre métallique ou poudre d'alliage stabilisée et procédé et cuve de réaction pour la produire

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UA102086C2 (ru) 2013-06-10
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CN101925427A (zh) 2010-12-22
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RU2010134800A (ru) 2012-02-27
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MX2010007826A (es) 2010-09-22
IL237346A0 (en) 2015-04-30
US8821610B2 (en) 2014-09-02
EP2394762A1 (fr) 2011-12-14
MY152942A (en) 2014-12-15
CA2712929A1 (fr) 2009-07-30
AU2009207739A1 (en) 2009-07-30
IL206966A (en) 2015-06-30
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JP5876651B2 (ja) 2016-03-02
US20150130121A1 (en) 2015-05-14
US9279617B2 (en) 2016-03-08
DE102008005781A1 (de) 2009-07-30
US20100272999A1 (en) 2010-10-28
AU2009207739B2 (en) 2013-03-07
WO2009092631A1 (fr) 2009-07-30
EP2247398B1 (fr) 2014-08-20
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