EP1558774B1 - Method and device for carrying out a tribochemical reaction - Google Patents

Method and device for carrying out a tribochemical reaction Download PDF

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Publication number
EP1558774B1
EP1558774B1 EP03773570A EP03773570A EP1558774B1 EP 1558774 B1 EP1558774 B1 EP 1558774B1 EP 03773570 A EP03773570 A EP 03773570A EP 03773570 A EP03773570 A EP 03773570A EP 1558774 B1 EP1558774 B1 EP 1558774B1
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Prior art keywords
reaction
titanium
metal
medium
faraday
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German (de)
French (fr)
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EP1558774A1 (en
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Peter Jörg Plath
Elisabeth Swart
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PLATH, PETER JOERG
SWART, ELISABETH
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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
    • C22B34/129—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 by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
    • 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
    • C22B34/1218—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 titanium or titanium compounds from ores or scrap by dry processes
    • C22B34/1222—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 titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
    • 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
    • C22B34/1281—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 carbon containing agents, e.g. C, CO, carbides

Definitions

  • the invention is in the field of tribochemical reactions and more particularly relates to the use of Faraday instabilities in carrying out a tribochemical reaction.
  • titanium tetrachloride is prepared by the Kroll process using coal and chlorine gas from the known titanium-containing minerals, e.g. Ilmenite or rutile in a rotary kiln or fluidized bed at temperatures of about 800 - 1000 ° C is produced.
  • the liquid titanium tetrachloride is then reduced after appropriate purification (crystallization and subsequent distillation at 136 ° C) with liquid magnesium at about 800 - 1000 ° C to titanium sponge.
  • the resulting magnesium chloride is washed out and electrolytically re-reduced to magnesium, which is recycled to the process.
  • the titanium sponge because of its large surface area, still binds larger amounts of oxygen which are not needed as an alloying ingredient in the intended metal to be produced.
  • the titanium sponge must be broken, crushed, pressed into electrodes and then remelted by arc melting in the arc to form compact metallic titanium. All the titanium process steps are carried out to avoid oxidation under inert gas (inert gas).
  • titanium tetrachloride which is obtained from titanium tetrachloride, is decomposed on thin, 1300 ° C. tungsten wires by the method of van Arkel and de Boer.
  • EP-A-744,234 describes a method for producing nanocrystalline metal powders.
  • the known method involves a painting or tribochemical activation of magnesium hydride.
  • the painting is carried out in a laboratory ball mill and using an organic solvent.
  • WO-A-95 08004 describes a method in which a nanostructured powder is produced by high-energy milling of ilmenite. To carry out the known method, a special form of ball mill is used.
  • the object of the invention is to provide an improved method and an improved apparatus for carrying out a tribochemical reaction in which the disadvantages of the prior art are avoided, in particular in titanium production.
  • the granular medium may either participate in the reaction or be inert to reaction products and starting materials.
  • the object of the invention is moreover, with the aid of the generation of Faraday instabilities in a granular (granules preferably with grain sizes of preferably 0.1 to 20 mm diameter) medium of the ores / minerals to produce a special tribochemical reaction situation, the direct conversion of Ore / mineral granules by reducing agent and halogen gas by heterogeneous catalytic reaction and oxidation of the reducing agent allowed.
  • the object of the invention in connection with the production of titanium is in particular, by means of the production of Faraday instabilities in a granular (granules preferably with grain sizes of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile) to produce a special tribochemical reaction situation, which involves the direct conversion of the ore / mineral granules to metallic titanium, which preferably has only usual accompanying elements, by means of reducing agents preferably carbon monoxide and halogen gas (preferably iodine or chlorine) by heterogeneous catalytic reaction and oxidation of the reducing agent, for example, the oxidation of carbon monoxide to carbon dioxide allowed.
  • reducing agents preferably carbon monoxide and halogen gas (preferably iodine or chlorine)
  • heterogeneous catalytic reaction preferably iodine or chlorine
  • the object of the invention in connection with the production of titanium dioxide is, with the help of the generation of Faraday instabilities in a granular (granules preferably with grain sizes of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile) a produce special tribochemical reaction situation, which allows the direct conversion of ore / mineral granules to titanium dioxide by means of reducing agent preferably carbon monoxide and halogen gas (preferably chlorine) by heterogeneous catalytic reaction and oxidation of the reducing agent, for example the oxidation of carbon monoxide to carbon dioxide.
  • reducing agent preferably carbon monoxide and halogen gas (preferably chlorine)
  • the invention includes the idea of producing Faraday instabilities in granular or spherical media by means of up / down motions in carrying out a tribochemical reaction.
  • the granular medium is moved up and down the gravity field to enter To bring a state in which the granular bed behaves similar to a liquid phase consisting of solid components. In this state, Faraday instabilities occur on the particles of the granular medium.
  • the Farady instabilities are created by moving a granular, granular or beaded medium up and down, forming tribochemical reaction conditions at the contact points / points of the constituents of the medium by means of Farady instabilities, at which the tribochemical reactions take place .
  • the use of Faraday instabilities in granular or spherical media for carrying out tribochemical reactions offers the advantage, compared to the classical method (Drekrohrofen or fluidized bed reactor) the advantage of being able to carry out the reaction in a thermodynamically much more favorable range.
  • the Faraday instabilities lead in the granular medium to a spatiotemporal pattern formation with zones of high mechanical energy. In these zones, even at relatively low temperatures, the tribochemical reactions in the area between or on the colliding particles of the granules or. the balls take place.
  • the advantage of using the Faraday instabilities for carrying out tribochemical reactions compared to the known fluidized bed method is in particular that in the granular, Faraday instabilities using fluidized bed energization areas arise in which the tribochemical reactions can proceed even at much lower temperatures than in a conventional Fluidized bed.
  • metal recovery process is that the reduction of metal oxide (ore) by coal and halogen gas is replaced by the much more effective heterogeneous catalytic gas-solid reaction between ore, reducing agent (eg carbon monoxide) and halogen gas to metal halide and carbon dioxide ,
  • An advantage of the process with regard to the production of titanium by the titanium tetraiodide process is that the very energy-consuming, multi-stage process of producing titanium from titanium ore (for example ilmenite or rutile) by means of a one-stage, very simple to handle titanium sponge. energy-saving process without an intermediate step is replaced by titanium sponge.
  • An advantage of the process with respect to the production of titanium white (titanium dioxide) according to the titanium tetrachloride method is that the multi-stage process can be replaced by a one-stage process (addition of oxygen to the titanium tetrachloride stream).
  • FIG. 1 shows a device 1 for utilizing Faraday instabilities for carrying out a tribochemical reaction.
  • the device 1 is particularly suitable for obtaining crude titanium (titanium tetrahalide) for further processing into titanium or titanium white (titanium dioxide) from titanium-containing ore / minerals.
  • the ore or minerals are applied to a horizontal plate or plate 9.
  • a moving device 5 By means of a moving device 5, the plate / the plate 9 is moved in the vertical direction.
  • a movement devices 5 in particular pneumatic, hydraulic cylinders or linear drives can be used.
  • the motion in the vertical is such that Faraday instability occurs in the granular ore or mineral.
  • the movement can take place in particular in a periodic or chaotic manner.
  • educt fluids can be introduced through bores in the reaction mixture.
  • these are gaseous halides and carbon monoxide as the reducing agent.
  • the reaction space of the device 1 is delimited from the environment. This is done in particular by a side wall of the reactor lower part 8, which is advantageously cylindrical, and by a cover 3, which is sealed in the parting plane 4 against the side wall of the reactor lower part 8.
  • the lid 3 can be flanged, while in the parting plane 4, a seal (not shown) is introduced.
  • at least one inlet 6 may be provided. This can be advantageously attached to the reactor base 8.
  • this is provided with at least one opening 2, which is advantageously attached to the lid 3 of the reactor.
  • heatable metal wires can be attached, in particular on the lid of the reactor, where titanium tetrahalide can precipitate and decompose.
  • titanium iodide these are, for example, tungsten wires.
  • a further opening may be provided to introduce oxygen to produce titanium dioxide from titanium tetrachloride into the reaction space.
  • this introduction can also be done only after the titanium tetrachloride has been removed from the reaction space after the reaction products have passed through the opening 2.
  • FIG. 2 shows a device 20 similar to the device 1 from FIG. 1 for using Faraday instabilities when carrying out tribochemical reactions. Same features marked with the same reference numerals.
  • the device 20 in FIG. 2 differs in particular from the device 1 according to FIG. 1 in that the movement device 5 is realized outside the reaction chamber of the device 20. This has the advantage that reaction products, intermediates and products can not corrosive or otherwise damage the moving devices. When designing the movement device 5, the higher load must be taken into account in this case.
  • the ground ores / minerals are placed on a plate that swings up and down in the vertical direction in the gravitational field to a state in which the granular bed behaves similar to a liquid phase consisting of solid constituents.
  • Faraday instabilities are formed at the interface of this liquid, granular layer to the (protective) gas phase, for example in the form of spatially stable wave patterns.
  • Inert gases preferably noble gases, preferably argon and helium, are preferably used as protective gas. If individual granular particles collide in the particularly excited regions of this layer, the gases in the reaction space can react with each other in a tribochemical manner at the joints. If, for example, titanium ores, titanium minerals are processed, titanium / titanium oxide is the end product sought.
  • the product of this reaction is initially a metal salt or complex.
  • the product of this reaction with titanium ores / titanium minerals is a titanium tetrahalide which sublimes or evaporates as a gas.
  • the sublimate can be mixed with oxygen at high temperature and oxidized to titanium dioxide.
  • the resulting chlorine gas can be recycled to the process.
  • the sublimate / steam is decomposed, for example, on electrically heated tungsten wires at about 1300 ° C. to form compact titanium and iodine.
  • the iodine can in turn be recycled back into the process.
  • the described method and the illustrated devices 1 and 20 can be used for the carbon-free production of metal and metal oxide from metal-containing ore.
  • a metal salt resp. creates a complex.
  • This metal salt / complex can then be further processed. Solutions of several metal salts can be separated in this case, for example, by means of a method which in the international patent application PCT / DE02 / 01377 is described.
  • the process described is also suitable for recovering (raw) titanium and titanium dioxide from the known titanium-containing minerals, for example ilmenite and rutile.
  • a reducing agent preferably carbon monoxide
  • a halogen preferably chlorine or iodine
  • the titanium tetrachloride or titanium tetraiodide is formed.
  • the titanium tetrachloride can then be processed in the known, traditional manner with magnesium to titanium in the form of titanium sponge. However, the titanium tetraiodide is sublimed, and with thermal decomposition, the pure titanium is precipitated therefrom without sponging.

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Abstract

The invention relates to a method and device for carrying out a tribochemical reaction, during which Faraday instabilities are produced by the spatial to-and-fro movement of a medium that is granular, grainy or made of balls. Tribochemical reaction conditions are produced with the aid of Faraday instabilities at points of contact of particles of the medium. The medium can either participate in the reaction or behave inertly with regard to the other educts. The method is suited for extracting (raw) titanium and titanium oxide from titaniferous minerals, for example, ilmenite and rutile.

Description

Die Erfindung liegt auf dem Gebiet tribochemischer Reaktionen und betrifft insbesondere eine Nutzung von Faraday-Instabilitäten beim Durchführen einer tribochemischen Reaktion.The invention is in the field of tribochemical reactions and more particularly relates to the use of Faraday instabilities in carrying out a tribochemical reaction.

Hintergrundbackground

Es ist bekannt, daß Titantetrachlorid nach dem Kroll-Verfahren mittels Kohle und Chlorgas aus den bekannten titanhaltigen Mineralien wie z.B. Ilmenit oder Rutil im Drehrohrofen oder im Wirbelschichtofen bei Temperaturen von ca. 800 - 1000 °C hergestellt wird. Das flüssige Titantetrachlorid wird dann nach entsprechender Reinigung (Kristallisation und anschließende Destillation bei 136° C) mit flüssigem Magnesium bei ca. 800 - 1000 °C zu Titanschwamm reduziert. Das hierbei entstehende Magnesiumchlorid wird ausgewaschen und elektrolytisch wieder zu Magnesium reduziert, das in den Prozeß zurückgeführt wird.It is known that titanium tetrachloride is prepared by the Kroll process using coal and chlorine gas from the known titanium-containing minerals, e.g. Ilmenite or rutile in a rotary kiln or fluidized bed at temperatures of about 800 - 1000 ° C is produced. The liquid titanium tetrachloride is then reduced after appropriate purification (crystallization and subsequent distillation at 136 ° C) with liquid magnesium at about 800 - 1000 ° C to titanium sponge. The resulting magnesium chloride is washed out and electrolytically re-reduced to magnesium, which is recycled to the process.

Der Titanschwamm enthält aufgrund seiner großen Oberfläche noch größere Mengen Sauerstoff gebunden, die nicht als Legierungsbestandteil im herzustellen beabsichtigten Metall benötigt werden. Der Titanschwamm muß gebrochen, zerkleinert, zu Elektroden gepreßt und dann im Lichtbogen mittels Zonenschmelzverfahren zu kompaktem metallischen Titan umgeschmolzen werden. Alle das Titan betreffenden Verfahrensschritte werden zur Vermeidung von Oxidation unter Schutzgas (Edelgas) ausgeführt.The titanium sponge, because of its large surface area, still binds larger amounts of oxygen which are not needed as an alloying ingredient in the intended metal to be produced. The titanium sponge must be broken, crushed, pressed into electrodes and then remelted by arc melting in the arc to form compact metallic titanium. All the titanium process steps are carried out to avoid oxidation under inert gas (inert gas).

Um besonders reines Titan herzustellen, wird nach dem Verfahren von van Arkel und de Boer Titantetrajodid, welches aus Titantetrachlorid gewonnen wird, an dünnen, 1300 °C heißen Wolframdrähten zersetzt.To produce particularly pure titanium, titanium tetrachloride, which is obtained from titanium tetrachloride, is decomposed on thin, 1300 ° C. tungsten wires by the method of van Arkel and de Boer.

In dem Dokument Popovich, A. et al., Journal of Alloys and Compounds, Bd. 190, Nr. 2, Seiten 143-147, 11. Januar 1993 , werden die physikalischen und chemischen Mechanismen untersucht, auf denen tribochemische Reaktionen von Metallen und Nichtmetallen basieren. Als Reaktionsraum für die tribochemischen Reaktionen wird eine Schwingmühle verwendet, welche mit dem Mahlgut gefüllt wird. Das Mahlgut umfaßt Pulver unterschiedlicher Metalle und Metalloxide.In the document Popovich, A. et al., Journal of Alloys and Compounds, Vol. 190, No. 2, pp. 143-147, Jan. 11, 1993 , investigates the physical and chemical mechanisms on which tribochemical reactions of metals and nonmetals are based. As a reaction space for the tribochemical reactions, a vibrating mill is used, which is filled with the material to be ground. The millbase comprises powders of different metals and metal oxides.

In dem Dokument EP-A-744 234 wird ein Verfahren zur Herstellung nanokristalliner Metallpulver beschrieben. Das bekannte Verfahren umfaßt eine Aufmalung bzw. tribochemische Aktivierung von Magnesiumhydrid. Die Ausmalung erfolgt in einer Laborkugelmühle und unter Verwendung eines organischen Lösungsmittels.In the document EP-A-744,234 describes a method for producing nanocrystalline metal powders. The known method involves a painting or tribochemical activation of magnesium hydride. The painting is carried out in a laboratory ball mill and using an organic solvent.

In dem Dokument WO-A-95 08004 wird ein Verfahren beschrieben, bei welchem mittels hochenergetischen Mahlens von Ilmenit ein nanostrukturiertes Pulver erzeugt wird. Zur Durchführung des bekannten Verfahrens wird eine spezielle Form einer Kugelmühle verwendet.In the document WO-A-95 08004 describes a method in which a nanostructured powder is produced by high-energy milling of ilmenite. To carry out the known method, a special form of ball mill is used.

Erfindunginvention

Aufgabe der Erfindung ist es, ein verbessertes Verfahren und eine verbesserte Vorrichtung zum Durchführen einer tribochemischen Reaktion anzugeben, bei denen die Nachteile des Standes Technik vermieden werden, insbesondere bei der Titanerzeugung.The object of the invention is to provide an improved method and an improved apparatus for carrying out a tribochemical reaction in which the disadvantages of the prior art are avoided, in particular in titanium production.

Es ist weiterhin Aufgabe der Erfindung, mit Hilfe der Erzeugung von Faraday-Instabilitäten in einem granularen (Granulate vorzugsweise mit Körnungen von vorzugsweise 0,1 bis 20 mm Durchmesser) Medium eine spezielle tribochemische Reaktionssituation zu erzeugen, die die Direktumwandlung des Eduktgemisches zu Produkten mit Hilfe tribochemischer Reaktionen erlaubt. Dabei kann das granulare Medium je nach angestrebter Reaktion entweder an der Reaktion teilnehmen oder gegenüber Reaktionsprodukten und Edukten inert sein.It is a further object of the invention to produce a special tribochemical reaction situation with the aid of the generation of Faraday instabilities in a granular (granules preferably having grain sizes of preferably 0.1 to 20 mm diameter) medium, which allows the direct conversion of the educt mixture to products by means of tribochemical reactions. Depending on the desired reaction, the granular medium may either participate in the reaction or be inert to reaction products and starting materials.

Aufgabe der Erfindung ist darüber hinaus es, mit Hilfe der Erzeugung von Faraday-Instabilitäten in einem granularen (Granulate vorzugsweise mit Körnungen von vorzugsweise 0,1 bis 20 mm Durchmesser) Medium der Erze/Mineralien eine spezielle tribochemische Reaktionssituation zu erzeugen, die die Direktumwandlung des Erz-/Mineralien-Granulats mittels Reduktionsmittel und Halogengas durch heterogene katalytische Reaktion und Oxidation des Reduktionsmittels gestattet.The object of the invention is moreover, with the aid of the generation of Faraday instabilities in a granular (granules preferably with grain sizes of preferably 0.1 to 20 mm diameter) medium of the ores / minerals to produce a special tribochemical reaction situation, the direct conversion of Ore / mineral granules by reducing agent and halogen gas by heterogeneous catalytic reaction and oxidation of the reducing agent allowed.

Aufgabe der Erfindung im Zusammenhang mit der Erzeugung von Titan ist es insbesondere, mit Hilfe der Erzeugung von Faraday-Instabilitäten in einem granularen (Granulate vorzugsweise mit Körnungen von 0,1 bis 20 mm Durchmesser) Medium der Erze/Mineralien (z.B. Ilmenit oder Rutil) eine spezielle tribochemische Reaktionssituation zu erzeugen, die die Direktumwandlung des Erz-/Mineralien-Granulats zu metallischem Titan, das vorzugsweise nur noch gebrauchsübliche Begleitelemente aufweist, mittels Reduktionsmittel vorzugsweise Kohlenmonoxid und Halogengas (vorzugsweise Jod oder Chlor) durch heterogene katalytische Reaktion und Oxidation des Reduktionsmittels, beispielsweise der Oxidation von Kohlenmonoxid zu Kohlendioxid gestattet.The object of the invention in connection with the production of titanium is in particular, by means of the production of Faraday instabilities in a granular (granules preferably with grain sizes of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile) to produce a special tribochemical reaction situation, which involves the direct conversion of the ore / mineral granules to metallic titanium, which preferably has only usual accompanying elements, by means of reducing agents preferably carbon monoxide and halogen gas (preferably iodine or chlorine) by heterogeneous catalytic reaction and oxidation of the reducing agent, for example, the oxidation of carbon monoxide to carbon dioxide allowed.

Aufgabe der Erfindung im Zusammenhang mit der Erzeugung von Titandioxid ist es, mit Hilfe der Erzeugung von Faraday-Instabilitäten in einem granularen (Granulate vorzugsweise mit Körnungen von 0,1 bis 20 mm Durchmesser) Medium der Erze/Mineralien (z.B. Ilmenit oder Rutil) eine spezielle tribochemische Reaktionssituation zu erzeugen, die die Direktumwandlung des Erz-/Mineralien-Granulats zu Titandioxid mittels Reduktionsmittel vorzugsweise Kohlenmonoxid und Halogengas (vorzugsweise Chlor) durch heterogene katalytische Reaktion und Oxidation des Reduktionsmittels, beispielsweise der Oxidation von Kohlenmonoxid zu Kohlendioxid gestattet.The object of the invention in connection with the production of titanium dioxide is, with the help of the generation of Faraday instabilities in a granular (granules preferably with grain sizes of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile) a produce special tribochemical reaction situation, which allows the direct conversion of ore / mineral granules to titanium dioxide by means of reducing agent preferably carbon monoxide and halogen gas (preferably chlorine) by heterogeneous catalytic reaction and oxidation of the reducing agent, for example the oxidation of carbon monoxide to carbon dioxide.

Die Aufgabe wird durch die unabhängigen Ansprüche gelöst.The object is solved by the independent claims.

Die Erfindung umfaßt den Gedanken, in granularen oder aus Kugeln bestehenden Medien Faraday-Instabilitäten mittels Auf-/Abbewegungen beim Durchführen einer tribochemischen Reaktion zu erzeugen. Das granulare Medium wird im Schwerefeld auf- und abbewegt, um in einen Zustand gebracht zu werden, bei dem die granulare Schüttung sich ähnlich einer flüssigen Phase verhält, die aus festen Bestandteilen besteht. In diesem Zustand treten Faraday-Instabilitäten an den Partikeln des granularen Mediums auf. Die Farady-Instabilitäten werden erzeugt, indem ein granulares, körniges oder aus Kugeln gebildetes Medium auf und ab bewegt wird, wobei mit Hilfe der Farady-Instabilitäten an Kontaktstellen/-punkten der Bestandteile des Mediums tribochemische Reaktionsbedingungen gebildet werden, bei denen die tribochemische Reaktionen abläuft. Die Nutzung der Faraday-Instabilitäten in granularen oder als Kugeln bestehenden Medien zur Durchführung von tribochemischen Reaktionen bietet gegenüber der klassischen Methodik (Drekrohrofen oder Wirbelschichtreaktor) den Vorteil, in einem thermodynamisch weitaus günstigeren Bereich die Reaktion durchführen zu können.The invention includes the idea of producing Faraday instabilities in granular or spherical media by means of up / down motions in carrying out a tribochemical reaction. The granular medium is moved up and down the gravity field to enter To bring a state in which the granular bed behaves similar to a liquid phase consisting of solid components. In this state, Faraday instabilities occur on the particles of the granular medium. The Farady instabilities are created by moving a granular, granular or beaded medium up and down, forming tribochemical reaction conditions at the contact points / points of the constituents of the medium by means of Farady instabilities, at which the tribochemical reactions take place , The use of Faraday instabilities in granular or spherical media for carrying out tribochemical reactions offers the advantage, compared to the classical method (Drekrohrofen or fluidized bed reactor) the advantage of being able to carry out the reaction in a thermodynamically much more favorable range.

Die Faraday-Instabilitäten führen in dem granularen Medium zu einer räumlichen bzw. raumzeitlichen Musterbildung mit Zonen hoher mechanischer Energie. In diesen Zonen können bereits bei vergleichsweise niedrigen Temperaturen die tribochemischen Reaktionen im Bereich zwischen bzw. an den zusammenstoßenden Teilchen des Granulats resp. der Kugeln stattfinden.The Faraday instabilities lead in the granular medium to a spatiotemporal pattern formation with zones of high mechanical energy. In these zones, even at relatively low temperatures, the tribochemical reactions in the area between or on the colliding particles of the granules or. the balls take place.

Der Vorteil der Nutzung der Faraday-Instabilitäten zur Durchführung von tribochemischen Reaktionen gegenüber dem bekannten Wirbelschichtverfahren besteht insbesondere darin, daß in der granularen, Faraday-Instabilitäten nutzenden Wirbelschicht Erregungsbereiche entstehen, in denen die tribochemische Reaktionen bereits bei wesentlich tieferen Temperaturen ablaufen können als in einer herkömmlichen Wirbelschicht.The advantage of using the Faraday instabilities for carrying out tribochemical reactions compared to the known fluidized bed method is in particular that in the granular, Faraday instabilities using fluidized bed energization areas arise in which the tribochemical reactions can proceed even at much lower temperatures than in a conventional Fluidized bed.

Ein Vorteil des Verfahrens beim Einsatz zur Metallgewinnung besteht darin, daß die Reduktion des Metalloxids (Erz) mittels Kohle und Halogengas durch die wesentlich effektivere heterogen katalytische Gas-Festkörper-Reaktion zwischen Erz, Reduktionsmittel (z.B. Kohlenmonoxid) und Halogengas zu Metallhalogenid und Kohlendioxid ersetzt wird.An advantage of the metal recovery process is that the reduction of metal oxide (ore) by coal and halogen gas is replaced by the much more effective heterogeneous catalytic gas-solid reaction between ore, reducing agent (eg carbon monoxide) and halogen gas to metal halide and carbon dioxide ,

Ein Vorteil des Verfahrens im Hinblick auf die Herstellung von Titan nach dem Titantetrajodid-Verfahren besteht darin, daß der sehr energieaufwendige, mehrstufige Prozeß der Herstellung von Titan aus Titanerz (z.B. Ilmenit oder Rutil) über den technisch sehr aufwendig zu handhabenden Titanschwamm durch einen einstufigen, energiesparenden Prozeß ohne einen Zwischenschritt über Titanschwamm ersetzt wird.An advantage of the process with regard to the production of titanium by the titanium tetraiodide process is that the very energy-consuming, multi-stage process of producing titanium from titanium ore (for example ilmenite or rutile) by means of a one-stage, very simple to handle titanium sponge. energy-saving process without an intermediate step is replaced by titanium sponge.

Ein Vorteil des Verfahrens im Hinblick auf die Herstellung von Titanweiß (Titandioxid) nach der Titantetrachlorid-Methode besteht darin, daß der mehrstufige Prozeß durch einen einstufigen Prozeß (Zugabe von Sauerstoff in den Titantetrachlorid-Strom) ersetzt werden kann.An advantage of the process with respect to the production of titanium white (titanium dioxide) according to the titanium tetrachloride method is that the multi-stage process can be replaced by a one-stage process (addition of oxygen to the titanium tetrachloride stream).

Ausführungsbeispieleembodiments

Die Erfindung wird im folgenden anhand von Ausführungsbeispielen unter Bezugnahme auf eine Zeichnung näher erläutert. Hierbei zeigen:

Figur 1
eine schematische Darstellung einer Vorrichtung zum Durchführen einer tribochemischen Reaktion, bei der Faraday-Instabilitäten genutzt werden; und
Figur 2
eine schematische Darstellung einer weiteren Vorrichtung zum Durchführen einer tribochemischen Reaktion, bei der Faraday-Instabilitäten genutzt werden.
The invention is explained below with reference to embodiments with reference to a drawing. Hereby show:
FIG. 1
a schematic representation of an apparatus for performing a tribochemical reaction in which Faraday instabilities are used; and
FIG. 2
a schematic representation of another device for performing a tribochemical reaction in which Faraday instabilities are used.

Figur 1 zeigt eine Vorrichtung 1 zur Nutzung von Faraday-Instabilitäten zum Durchführen einer tribochemischen Reaktion. Die Vorrichtung 1 ist insbesondere geeignet zur Gewinnung von Rohtitan (Titantetrahalogenid) zur weiteren Verarbeitung zu Titan oder Titanweiß (Titandioxid) aus titanhaltigem Erz/Mineralien.FIG. 1 shows a device 1 for utilizing Faraday instabilities for carrying out a tribochemical reaction. The device 1 is particularly suitable for obtaining crude titanium (titanium tetrahalide) for further processing into titanium or titanium white (titanium dioxide) from titanium-containing ore / minerals.

Zur Durchführung des Verfahrens wird auf einer horizontalen Platte oder einem horizontalen Teller 9 das Erz oder die Mineralien aufgebracht. Mittels einer Bewegungsvorrichtung 5 wird die Platte/der Teller 9 in lotrechter Richtung bewegt. Als Bewegungsvorrichtungen 5 können insbesondere Pneumatik-, Hydraulikzylinder oder Linearantriebe eingesetzt werden. Die Bewegung in der Lotrechten erfolgt dermaßen, daß in dem granularen Erz oder Mineral eine Faraday-Instabilität auftritt. Die Bewegung kann insbesondere in periodischer oder chaotischer Weise erfolgen.To carry out the process, the ore or minerals are applied to a horizontal plate or plate 9. By means of a moving device 5, the plate / the plate 9 is moved in the vertical direction. As a movement devices 5 in particular pneumatic, hydraulic cylinders or linear drives can be used. The motion in the vertical is such that Faraday instability occurs in the granular ore or mineral. The movement can take place in particular in a periodic or chaotic manner.

Mittels einer Zuführungseinrichtung 7 können Edukt-Fluide durch Bohrungen in das Reaktionsgemisch eingeleitet werden. Im Falle der Titan oder Titandioxidgewinnung handelt es sich hierbei um gasförmige Halogenide und Kohlenmonoxid als Reduktionsmittel. Der Reaktionsraum der Vorrichtung 1 wird gegenüber der Umwelt abgegrenzt. Dies geschieht insbesondere durch eine Seitenwand des Reaktorunterteiles 8, die vorteilhafter Weise zylindrisch ausgebildet wird, und durch einen Deckel 3, der in der Trennebene 4 gegen die Seitenwand des Reaktorunterteiles 8 abgedichtet wird. Beispielsweise kann der Deckel 3 angeflanscht werden, während in der Trennebene 4 eine Dichtung (nicht dargestellt) eingebracht wird. Um Schutzgase in dem Reaktionsraum einzubringen, kann zumindest ein Einlaß 6 vorgesehen sein. Dieser kann vorteilhafterweise am Reaktorunterteil 8 angebracht sein.By means of a feed device 7 educt fluids can be introduced through bores in the reaction mixture. In the case of titanium or titanium dioxide production, these are gaseous halides and carbon monoxide as the reducing agent. The reaction space of the device 1 is delimited from the environment. This is done in particular by a side wall of the reactor lower part 8, which is advantageously cylindrical, and by a cover 3, which is sealed in the parting plane 4 against the side wall of the reactor lower part 8. For example, the lid 3 can be flanged, while in the parting plane 4, a seal (not shown) is introduced. To protective gases in the reaction space, at least one inlet 6 may be provided. This can be advantageously attached to the reactor base 8.

Um die gasförmige Reaktionsprodukte aus dem Reaktionsraum abzuziehen, ist dieser mit zumindest einer Öffnung 2 versehen, die vorteilhafter Weise am Deckel 3 des Reaktors angebracht wird. Anstelle der Öffnung 2 oder in Ergänzung hierzu können heizbare Metalldrähte angebracht sein, insbesondere am Deckel des Reaktors, an denen Titantetrahalogenid sich niederschlagen und zersetzen kann. Im Falle von Titanjodid handelt es sich hierbei zum Beispiel um Wolframdrähte.To withdraw the gaseous reaction products from the reaction space, this is provided with at least one opening 2, which is advantageously attached to the lid 3 of the reactor. Instead of the opening 2 or in addition heatable metal wires can be attached, in particular on the lid of the reactor, where titanium tetrahalide can precipitate and decompose. In the case of titanium iodide, these are, for example, tungsten wires.

Eine weitere Öffnung (nicht dargestellt) kann vorgesehen werden, um Sauerstoff zur Herstellung von Titandioxid aus Titantetrachlorid in den Reaktionsraum einzuleiten. Dieses Einleiten kann allerdings auch erst nachgeschaltet - nach dem Abziehen des Titantetrachlorids aus dem Reaktionsraum - geschehen, nachdem die Reaktionsprodukte die Öffnung 2 passiert haben.A further opening (not shown) may be provided to introduce oxygen to produce titanium dioxide from titanium tetrachloride into the reaction space. However, this introduction can also be done only after the titanium tetrachloride has been removed from the reaction space after the reaction products have passed through the opening 2.

Figur 2 zeigt eine zur Vorrichtung 1 aus Figur 1 ähnliche Vorrichtung 20 zur Nutzung von Faraday-Instabilitäten beim Durchführen von tribochemischen Reaktionen. Gleiche Merkmale mit gleichen Bezugszeichen gekennzeichnet. Die Vorrichtung 20 in Figur 2 unterscheidet sich insbesondere dadurch von der Vorrichtung 1 nach Figur 1, daß die Bewegungsvorrichtung 5 außerhalb der Reaktionskammer der Vorrichtung 20 realisiert ist. Dies hat den Vorteil, das Reaktionsedukte, -zwischenprodukte und -produkte die Bewegungsvorrichtungen nicht korrosiv oder anderweitig schädigen können. Bei der Auslegung der Bewegungseinrichtung 5 ist in diesen Fall die höhere Belastung zu berücksichtigen.FIG. 2 shows a device 20 similar to the device 1 from FIG. 1 for using Faraday instabilities when carrying out tribochemical reactions. Same features marked with the same reference numerals. The device 20 in FIG. 2 differs in particular from the device 1 according to FIG. 1 in that the movement device 5 is realized outside the reaction chamber of the device 20. This has the advantage that reaction products, intermediates and products can not corrosive or otherwise damage the moving devices. When designing the movement device 5, the higher load must be taken into account in this case.

Die gemahlenen Erze/Mineralien werden auf einem in lotrechter Richtung im Schwerefeld auf- und abschwingenden Teller in einen Zustand gebracht, bei dem die granulare Schüttung sich ähnlich einer flüssigen Phase verhält, die aus festen Bestandteilen besteht. Dabei bilden sich an der Grenzfläche dieser flüssigen, granularen Schicht zur (Schutz)-Gasphase Faraday-Instabilitäten aus, zum Beispiel in Form räumlich stabiler Wellenmuster. Als Schutzgas werden hierbei vorzugsweise inerte Gase, vorzugsweise Edelgase, vorzugsweise Argon und Helium eingesetzt. Prallen in den besonders erregten Bereichen dieser Schicht einzelne granulare Teilchen aufeinander, dann können die im Reaktionsraum befindlichen Gase tribochemisch an den Stoßstellen katalytisch miteinander reagieren. Werden beispielsweise Titanerze, Titanmineralien aufbereitet wird Titan/Titanoxid als Endprodukt angestrebt.The ground ores / minerals are placed on a plate that swings up and down in the vertical direction in the gravitational field to a state in which the granular bed behaves similar to a liquid phase consisting of solid constituents. In the process, Faraday instabilities are formed at the interface of this liquid, granular layer to the (protective) gas phase, for example in the form of spatially stable wave patterns. Inert gases, preferably noble gases, preferably argon and helium, are preferably used as protective gas. If individual granular particles collide in the particularly excited regions of this layer, the gases in the reaction space can react with each other in a tribochemical manner at the joints. If, for example, titanium ores, titanium minerals are processed, titanium / titanium oxide is the end product sought.

Das Produkt dieser Reaktion ist zunächst ein Metallsalz bzw. -komplex. Das Produkt dieser Reaktion mit Titanerzen/Titanmineralien ist ein Titantetrahalogenid, das als Gas sublimiert bzw. verdampft.The product of this reaction is initially a metal salt or complex. The product of this reaction with titanium ores / titanium minerals is a titanium tetrahalide which sublimes or evaporates as a gas.

Soll beispielsweise im Fall des Titantetrachlorids daraus direkt Titandioxid hergestellt werden, kann das Sublimat bei hoher Temperatur mit Sauerstoff vermengt und zu Titandioxid oxidiert werden. Das hierbei entstehende Chlorgas kann in den Prozeß zurückgeführt werden.If, for example, titanium dioxide is to be prepared directly from titanium tetrachloride in this case, the sublimate can be mixed with oxygen at high temperature and oxidized to titanium dioxide. The resulting chlorine gas can be recycled to the process.

Soll im Fall von Titantetrajodid daraus direkt metallisches Titan hergestellt werden, wird das Sublimat/der Dampf zum Beispiel an elektrisch geheizten Wolframdrähten bei ca. 1300 °C zu kompaktem Titan und Jod zersetzt. Das Jod kann wiederum in den Prozeß zurückgeführt werden.If, in the case of titanium tetraiodide, metallic titanium is to be directly produced therefrom, the sublimate / steam is decomposed, for example, on electrically heated tungsten wires at about 1300 ° C. to form compact titanium and iodine. The iodine can in turn be recycled back into the process.

Das beschriebene Verfahren und die erläuterten Vorrichtungen 1 und 20 können zur kohlefreien Herstellung von Metall und Metalloxid aus metallhaltigem Erz eingesetzt werden. In einer heterogenen Gas-Festkörper-Reaktion wird dabei mit einem Reduktionsmittel und einem Halogen ein Metallsalz resp. ein Komplex erzeugt. Dieses Metallsalz/dieser Komplex läßt sich dann weiterverarbeiten. Lösungen mehrerer Metallsalze lassen sich hierbei beispielsweise mit Hilfe eines Verfahrens trennen, welches in der internationalen Patentanmeldung PCT/DE02/01377 beschrieben ist.The described method and the illustrated devices 1 and 20 can be used for the carbon-free production of metal and metal oxide from metal-containing ore. In a heterogeneous gas-solid-state reaction with a reducing agent and a halogen, a metal salt resp. creates a complex. This metal salt / complex can then be further processed. Solutions of several metal salts can be separated in this case, for example, by means of a method which in the international patent application PCT / DE02 / 01377 is described.

Beispielsweise eignet sich das beschriebene Verfahren, wie oben erläutert, auch zur Gewinnung von (Roh-)Titan und Titandioxid aus den bekannten titanhaltigen Mineralien, beispielsweise Ilmenit und Rutil. In einer heterogenen Gas-Festkörper-Reaktion mit einem Reduktionsmittel vorzugsweise Kohlenmonoxid, und einem Halogen bildet sich daraus das entsprechende Titanhalogenid. Wird vorteilhafterweise Chlor oder Jod als Halogen in der Gas-Festkörperreaktion neben Kohlenmonoxid eingesetzt, entsteht dabei das Titantetrachlorid bzw. Titantetrajodid. Das Titantetrachlorid kann dann in der bekannten, traditionellen Weise mit Magnesium zu Titan in Form von Titanschwamm verarbeitet werden. Das Titantetrajodid jedoch wird sublimiert und unter thermischer Zersetzung wird daraus das Reintitan, ohne das Schwammbildung auftritt, abgeschieden.For example, as described above, the process described is also suitable for recovering (raw) titanium and titanium dioxide from the known titanium-containing minerals, for example ilmenite and rutile. In a heterogeneous gas-solid reaction with a reducing agent, preferably carbon monoxide, and a halogen, the corresponding titanium halide is formed therefrom. If, advantageously, chlorine or iodine is used as the halogen in the gas-solid reaction in addition to carbon monoxide, the titanium tetrachloride or titanium tetraiodide is formed. The titanium tetrachloride can then be processed in the known, traditional manner with magnesium to titanium in the form of titanium sponge. However, the titanium tetraiodide is sublimed, and with thermal decomposition, the pure titanium is precipitated therefrom without sponging.

Die in der vorstehenden Beschreibung, den Ansprüchen und der Zeichnung offenbarten Merkmale der Erfindung können sowohl einzeln als auch in beliebiger Kombination für die Verwirklichung der Erfindung in ihren verschiedenen Ausführungsformen von Bedeutung sein.The features of the invention disclosed in the foregoing description, the claims and the drawings can be used individually or in any combination for the Realization of the invention in its various embodiments of importance.

Claims (9)

  1. A method for carrying out a tribochemical reaction, characterized in that Faraday instabilities are generated by setting a medium, which is granular, grain-like or formed of balls, in spatial to-and-fro motion, tribochemical reactions being carried out by means of the Faraday instabilities at contact areas and contact points of particles of the medium.
  2. The method according to claim 1, characterized in that shaped articles, in particular balls, which do not participate in the reaction are used as the medium for carrying out the reaction.
  3. The method according to claim 1 or 2, characterized in that inert metal balls, in particular stainless steel balls, are used.
  4. The method according to claim 1, characterized in that media which participate in the reaction, in particular ores, are used as media for carrying out the reaction.
  5. The use of the method according to any one of claims 1 to 4 for the carbon-free production of metal and metal oxide.
  6. The use of the method according to any one of claims 1 to 4 for the carbon-free production of titanium and titanium dioxide.
  7. The use of the method according to any one of claims 1 to 4 for the carbon-free production of metal complexes.
  8. The use of the method according to any one of claims 1 or 4 for the carbon-free production of a metal and a metal oxide, individual fractions of the material produced from the ore being isolated in order to produce a metal, a metal salt or a metal oxide therefrom.
  9. A device for carrying out the method according to any one of claims 1 to 4 having an enclosed reaction chamber, in which, within a cover (3), a horizontal supporting surface (9) is formed for a medium which is granular, grain-like or formed of balls, the horizontal supporting surface (9) being coupled to a movement apparatus, with which the medium which is granular, grain-like or formed of balls may be moved to and fro in order to produce Faraday instabilities on particles of the medium for the purpose of a tribochemical reaction and, furthermore, at least one of the following features being provided: an opening (2) in the cover (3), which is configured to withdraw reaction products from the reaction chamber, and heatable metal wires on which titanium tetrahalide can settle and decompose, which wires are optionally arranged on the cover (3).
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MELO F.; UMBANHOWAR P.B.; SWINNEY H.L.: "Hexagons, Kinks, and Disorder in Oscillated Granular Layers", PHYSICAL REVIEW LETTERS, vol. 75, no. 21, 20 November 1995 (1995-11-20), pages 3838 - 3842 *

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