EP1558774A1 - Method and device for carrying out a tribochemical reaction - Google Patents

Method and device for carrying out a tribochemical reaction

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Publication number
EP1558774A1
EP1558774A1 EP03773570A EP03773570A EP1558774A1 EP 1558774 A1 EP1558774 A1 EP 1558774A1 EP 03773570 A EP03773570 A EP 03773570A EP 03773570 A EP03773570 A EP 03773570A EP 1558774 A1 EP1558774 A1 EP 1558774A1
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EP
European Patent Office
Prior art keywords
reaction
titanium
granular
medium
metal
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
EP03773570A
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German (de)
French (fr)
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EP1558774B1 (en
Inventor
Peter Jörg Plath
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PLATH, PETER JOERG
SWART, ELISABETH
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Plath Peter Jorg
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Publication of EP1558774A1 publication Critical patent/EP1558774A1/en
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Classifications

    • 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 relates in particular to the use of Faraday instabilities when carrying out a tribochemical reaction.
  • titanium tetrachloride can be obtained from the known titanium-containing minerals such as e.g. Ilmenite or rutile is produced in a rotary kiln or in a fluidized bed furnace at temperatures of approx. 800 - 1000 ° C. After appropriate cleaning (crystallization and subsequent distillation at 136 ° C), the liquid titanium tetrachloride is then reduced to titanium sponge with liquid magnesium at approx. 800 - 1000 ° C. The resulting magnesium chloride is washed out and electrolytically reduced again to magnesium, which is returned to the process.
  • the known titanium-containing minerals such as e.g. Ilmenite or rutile is produced in a rotary kiln or in a fluidized bed furnace at temperatures of approx. 800 - 1000 ° C. After appropriate cleaning (crystallization and subsequent distillation at 136 ° C), the liquid titanium tetrachloride is then reduced to titanium sponge with liquid magnesium at approx. 800 - 1000 ° C. The resulting magnesium chloride is
  • the titanium sponge Due to its large surface area, the titanium sponge contains even larger amounts of oxygen bound, which are not required as an alloy component in the metal to be produced.
  • the titanium sponge has to be broken, crushed, pressed into electrodes and then remelted in an arc using the zone melting process to form compact metallic titanium. All titanium-related steps are carried out under protective gas (inert gas) to avoid oxidation.
  • titanium tetraiodide which is obtained from titanium tetrachloride, is decomposed on thin, 1300 ° C hot tungsten wires using the van Arkel and de Boer process.
  • the object of the invention is to provide an improved method and an improved device for carrying out a tribochemical reaction in which the disadvantages of the prior art are avoided, in particular in the production of titanium.
  • the granular medium can either participate in the reaction or be inert to reaction products and starting materials.
  • the object of the invention is also to generate a special tribochemical reaction situation with the aid of the generation of Faraday instabilities in a granular (granules preferably with grains of preferably 0.1 to 20 mm diameter) of the ores / minerals, which the direct conversion of the Ore / mineral granules permitted by means of reducing agents and halogen gas by heterogeneous catalytic reaction and oxidation of the reducing agent.
  • the object of the invention in connection with the production of titanium is, in particular, with the aid of the generation of Faraday instabilities in a granular (preferably granules with a grain size of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile) to produce a special tribochemical reaction situation, which the direct conversion of the ore / mineral granulate to metallic titanium, which preferably only has customary accompanying elements, using a reducing agent, 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.
  • a reducing agent preferably carbon monoxide and halogen gas (preferably iodine or chlorine)
  • the object of the invention in connection with the production of titanium dioxide is, with the aid of the production of Faraday instabilities in a granular (preferably granules with a grain size of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile ) to produce a special tribochemical reaction situation which allows the direct conversion of the ore / mineral granules to titanium dioxide by means of a 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.
  • a reducing agent preferably carbon monoxide and halogen gas (preferably chlorine)
  • the invention encompasses the idea in granular or spherical media
  • the granular medium is moved up and down in the gravitational field in order to to be brought into 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 generated by moving a granular, granular or spherical medium up and down, with the help of the Farady instabilities at contact points / points of the components of the medium forming tribochemical reaction conditions under which the tribochemical Reactions expires.
  • the Faraday instabilities lead to a spatial or spatio-temporal pattern formation with zones of high mechanical energy in the granular medium. In these zones, even at comparatively low temperatures, the tribochemical reactions in the area between or on the colliding particles of the granulate or. of the balls take place.
  • the advantage of using the Faraday instabilities to carry out tribochemical reactions over the known fluidized bed process is, in particular, that in the granular fluidized bed using Faraday instabilities, excitation areas arise in which the tribochemical reactions can take place at much lower temperatures than in a conventional one Fluidized bed.
  • An advantage of the method when used for metal extraction is that the reduction of the metal oxide (ore) by means of coal and halogen gas is replaced by the much more effective heterogeneous catalytic gas-solid reaction between ore, reducing agent (e.g. carbon monoxide) and halogen gas to metal halide and carbon dioxide ,
  • reducing agent e.g. carbon monoxide
  • One advantage of the process with regard to the production of titanium by the titanium tetrajodide process is that the very energy-intensive, multi-stage process of producing titanium from titanium ore (eg ilmenite or rutile) via the titanium sponge, which is technically very complex to handle, by means of a single-stage, energy-saving process is replaced without an intermediate step over titanium sponge.
  • An advantage of the process with regard to the production of titanium white (titanium dioxide) by the titanium tetrachloride method is that the multi-stage process can be replaced by a one-stage process (addition of oxygen in the titanium tetrachloride stream).
  • Figure 1 is a schematic representation of a device for performing a tribochemical reaction in which Faraday instabilities are used.
  • Figure 2 is a schematic representation of another device for performing a tribochemical reaction in which Faraday instabilities are used.
  • FIG. 1 shows a device 1 for using Faraday instabilities to carry out a tribochemical reaction.
  • the device 1 is particularly suitable for the extraction of raw titanium (titanium tetrahalide) for further processing to titanium or titanium white (titanium dioxide) from titanium-containing ore / minerals.
  • the ore or minerals are applied to a horizontal plate or plate 9.
  • the plate / plate 9 is moved in the vertical direction by means of a movement device 5.
  • Pneumatic, hydraulic cylinders or linear drives can be used in particular as movement devices 5.
  • the vertical movement is such that Faraday instability occurs in the granular ore or mineral.
  • the movement can take place in a periodic or chaotic manner in particular.
  • educt fluids can be introduced into the reaction mixture through bores.
  • these are gaseous halides and carbon monoxide as reducing agents.
  • the reaction space of the device 1 is delimited from the environment. This is done in particular by a side wall of the lower reactor 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 lower reactor part 8.
  • the cover 3 can be flanged while a seal (not shown) is introduced in the parting plane 4.
  • at least one inlet 6 may be provided. This can advantageously be attached to the lower part 8 of the reactor.
  • this is provided with at least one opening 2, which is advantageously made on the cover 3 of the reactor.
  • heatable metal wires can be attached, in particular on the cover of the reactor, on which titanium tetrahalide can precipitate and decompose.
  • titanium iodide these are, for example, tungsten wires.
  • a further opening can be provided in order to introduce oxygen into the reaction space for the production of titanium dioxide from titanium tetrachloride.
  • this introduction can also only take place downstream - after the titanium tetrachloride has been drawn off from the reaction space - after the reaction products have passed through the opening 2.
  • FIG. 2 shows a device 20, similar to device 1 from FIG. 1, for using Faraday instabilities when carrying out tribochemical reactions. Identical features are identified by the same reference symbols.
  • 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 cannot damage the movement devices in a corrosive or other way. In this case, the higher load must be taken into account when designing the movement device 5.
  • the ground ores / minerals are brought into a state on a plate which swings up and down in the vertical direction in the gravitational field, in which the granular bed behaves similarly to a liquid phase which consists of solid components.
  • granular layer with the (protective) gas phase Faraday instabilities form, for example in the form of spatially stable wave patterns.
  • Inert gases preferably noble gases, preferably argon and helium, are preferably used as the protective gas. If individual granular particles collide in the particularly excited areas of this layer, the gases in the reaction space can react catalytically with one another tribochemically at the joints. If, for example, titanium ores and titanium minerals are processed, titanium / titanium oxide will be the end product.
  • 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 vaporizes as a gas.
  • the sublimate can be mixed with oxygen at high temperature and oxidized to titanium dioxide.
  • the resulting chlorine gas can be returned to the process.
  • the sublimate / steam is decomposed, for example on electrically heated tungsten wires, at approximately 1300 ° C to form compact titanium and iodine.
  • the iodine can in turn be returned to the process.
  • the described method and the explained devices 1 and 20 can be used for the carbon-free production of metal and metal oxide from metal-containing ore.
  • a metal salt or. created a complex In a heterogeneous gas-solid reaction, a metal salt or. created a complex. This metal salt / complex can then be processed further. Solutions of several metal salts can be separated here, for example, using a method which is described in the international patent application PCT / DE02 / 01377.
  • the process described is also suitable for the extraction of (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
  • chlorine or iodine is advantageously used as 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 a titanium sponge. However, the titanium tetraiodide is sublimed and the pure titanium is deposited therefrom with thermal decomposition, without the formation of sponges.

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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

Verfahren und Vorrichtung zum Durchführen einer tribochemischen Reaktion Method and device for carrying out a tribochemical reaction
Die Erfindung liegt auf dem Gebiet tribochemischer Reaktionen und betrifft insbesondere eine Nutzung von Faraday-Instabilitäten beim Durchfuhren einer tribochemischen Reaktion.The invention is in the field of tribochemical reactions and relates in particular to the use of Faraday instabilities when carrying out a tribochemical reaction.
Hintergrundbackground
Es ist bekannt, daß Titantetrachlorid nach dem Kroll-Nerfahren 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 can be obtained from the known titanium-containing minerals such as e.g. Ilmenite or rutile is produced in a rotary kiln or in a fluidized bed furnace at temperatures of approx. 800 - 1000 ° C. After appropriate cleaning (crystallization and subsequent distillation at 136 ° C), the liquid titanium tetrachloride is then reduced to titanium sponge with liquid magnesium at approx. 800 - 1000 ° C. The resulting magnesium chloride is washed out and electrolytically reduced again to magnesium, which is returned 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 Nerfahrensschritte werden zur Vermeidung von Oxidation unter Schutzgas (Edelgas) ausgeführt.Due to its large surface area, the titanium sponge contains even larger amounts of oxygen bound, which are not required as an alloy component in the metal to be produced. The titanium sponge has to be broken, crushed, pressed into electrodes and then remelted in an arc using the zone melting process to form compact metallic titanium. All titanium-related steps are carried out under protective gas (inert gas) to avoid oxidation.
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.In order to produce particularly pure titanium, titanium tetraiodide, which is obtained from titanium tetrachloride, is decomposed on thin, 1300 ° C hot tungsten wires using the van Arkel and de Boer process.
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 device for carrying out a tribochemical reaction in which the disadvantages of the prior art are avoided, in particular in the production of titanium.
Es ist weiterhin Aufgabe der Erfindung, mit Hilfe der Erzeugung von Faraday-Instabilitäten in einem granulären (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 granuläre 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 with a grain size of preferably 0.1 to 20 mm diameter), which allows the direct conversion of the starting material mixture to products using tribochemical reactions. Depending on the desired reaction, the granular medium can 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 granulären (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 also to generate a special tribochemical reaction situation with the aid of the generation of Faraday instabilities in a granular (granules preferably with grains of preferably 0.1 to 20 mm diameter) of the ores / minerals, which the direct conversion of the Ore / mineral granules permitted by means of reducing agents and halogen gas by heterogeneous catalytic reaction and oxidation of the reducing agent.
Aufgabe der Erfindung im Zusammenhang mit der Erzeugung von Titan ist es insbesondere, mit Hilfe der Erzeugung von Faraday-Instabilitäten in einem granulären (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, with the aid of the generation of Faraday instabilities in a granular (preferably granules with a grain size of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile) to produce a special tribochemical reaction situation, which the direct conversion of the ore / mineral granulate to metallic titanium, which preferably only has customary accompanying elements, using a reducing agent, 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.
Aufgabe der Erfindung im Zusammenhang mit der Erzeugung von Titandioxid ist es, mit Hil- fe der Erzeugung von Faraday-Instabilitäten in einem granulären (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 Reakti- on 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 aid of the production of Faraday instabilities in a granular (preferably granules with a grain size of 0.1 to 20 mm diameter) medium of the ores / minerals (eg ilmenite or rutile ) to produce a special tribochemical reaction situation which allows the direct conversion of the ore / mineral granules to titanium dioxide by means of a 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 task is solved by the independent claims.
Die Erfindung umfaßt den Gedanken, in granulären oder aus Kugeln bestehenden MedienThe invention encompasses the idea in granular or spherical media
Faraday-Instabilitäten mittels Auf-/Abbewegungen beim Durchführen einer tribochemischen Reaktion zu erzeugen. Das granuläre Medium wird im Schwerefeld auf- und abbewegt, um in einen Zustand gebracht zu werden, bei dem die granuläre Schüttung sich ähnlich einer flüssigen Phase verhält, die aus festen Bestandteilen besteht. In diesem Zustand treten Faraday- Instabilitäten an den Partikeln des granulären Mediums auf. Die Farady-Instabilitäten werden erzeugt, indem ein granuläres, körniges oder aus Kugeln gebildetes Medium auf und ab be- wegt 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 granulären 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.To generate Faraday instabilities using up / down movements when performing a tribochemical reaction. The granular medium is moved up and down in the gravitational field in order to to be brought into 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 generated by moving a granular, granular or spherical medium up and down, with the help of the Farady instabilities at contact points / points of the components of the medium forming tribochemical reaction conditions under which the tribochemical Reactions expires. The use of the Faraday instabilities in granular or spherical media for carrying out tribochemical reactions offers the advantage over the classic method (rotary tube furnace or fluidized bed reactor) that the reaction can be carried out in a thermodynamically far more favorable range.
Die Faraday-Instabilitäten führen in dem granulären 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 to a spatial or spatio-temporal pattern formation with zones of high mechanical energy in the granular medium. In these zones, even at comparatively low temperatures, the tribochemical reactions in the area between or on the colliding particles of the granulate or. of 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 granulären, 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 to carry out tribochemical reactions over the known fluidized bed process is, in particular, that in the granular fluidized bed using Faraday instabilities, excitation areas arise in which the tribochemical reactions can take place at much lower temperatures than in a conventional one 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 method when used for metal extraction is that the reduction of the metal oxide (ore) by means of coal and halogen gas is replaced by the much more effective heterogeneous catalytic gas-solid reaction between ore, reducing agent (e.g. carbon monoxide) and halogen gas to metal halide and carbon dioxide ,
Ein Vorteil des Verfahrens im Hinblick auf die Herstellung von Titan nach dem Titantetrajo- did- 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. 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.One advantage of the process with regard to the production of titanium by the titanium tetrajodide process is that the very energy-intensive, multi-stage process of producing titanium from titanium ore (eg ilmenite or rutile) via the titanium sponge, which is technically very complex to handle, by means of a single-stage, energy-saving process is replaced without an intermediate step over titanium sponge. An advantage of the process with regard to the production of titanium white (titanium dioxide) by the titanium tetrachloride method is that the multi-stage process can be replaced by a one-stage process (addition of oxygen in the titanium tetrachloride stream).
Ausführungsbeispieleembodiments
Die Erfindung wird im folgenden anhand von Ausführungsbeispielen unter Bezugnahme auf eine Zeichnung näher erläutert. Hierbei zeigen:The invention is explained in more detail below using exemplary embodiments with reference to a drawing. Here show:
Figur 1 eine schematische Darstellung einer Vorrichtung zum Durchfuhren einer tribochemischen Reaktion, bei der Faraday-Instabilitäten genutzt werden; undFigure 1 is a schematic representation of a device for performing a tribochemical reaction in which Faraday instabilities are used; and
Figur 2 eine schematische Darstellung einer weiteren Vorrichtung zum Durchführen einer tribochemischen Reaktion, bei der Faraday-Instabilitäten genutzt werden.Figure 2 is 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 using Faraday instabilities to carry out a tribochemical reaction. The device 1 is particularly suitable for the extraction of raw titanium (titanium tetrahalide) for further processing to 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 Bewegungs Vorrichtung 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 granulären Erz oder Mineral eine Faraday-Instabilität auftritt. Die Bewegung kann insbesondere in periodischer oder chaotischer Weise erfolgen.To carry out the method, the ore or minerals are applied to a horizontal plate or plate 9. The plate / plate 9 is moved in the vertical direction by means of a movement device 5. Pneumatic, hydraulic cylinders or linear drives can be used in particular as movement devices 5. The vertical movement is such that Faraday instability occurs in the granular ore or mineral. The movement can take place in a periodic or chaotic manner in particular.
Mittels einer Zufürmmgseinrichtung 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 Reaktions- räum 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 Schutz- gase in dem Reaktionsraum einzubringen, kann zumindest ein Einlaß 6 vorgesehen sein. Dieser kann vorteilhafterweise am Reaktorunterteil 8 angebracht sein.Using a feed device 7, educt fluids can be introduced into the reaction mixture through bores. In the case of titanium or titanium dioxide extraction, these are gaseous halides and carbon monoxide as reducing agents. The reaction space of the device 1 is delimited from the environment. This is done in particular by a side wall of the lower reactor 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 lower reactor part 8. For example, the cover 3 can be flanged while a seal (not shown) is introduced in the parting plane 4. To protect Introduce gases in the reaction chamber, at least one inlet 6 may be provided. This can advantageously be attached to the lower part 8 of the reactor.
Um die gasförmige Reaktionsprodukte aus dem Reaktionsraum abzuziehen, ist dieser mit zumindest einer Öffnung 2 versehen, die vorteilhafter Weise am Deckel 3 des Reaktors ange- bracht 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, hu Falle von Titanjodid handelt es sich hierbei zum Beispiel um Wolframdrähte.In order to withdraw the gaseous reaction products from the reaction space, this is provided with at least one opening 2, which is advantageously made on the cover 3 of the reactor. Instead of the opening 2 or in addition to this, heatable metal wires can be attached, in particular on the cover of the reactor, on which 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 Herstel- lung 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) can be provided in order to introduce oxygen into the reaction space for the production of titanium dioxide from titanium tetrachloride. However, this introduction can also only take place downstream - after the titanium tetrachloride has been drawn off 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 device 1 from FIG. 1, for using Faraday instabilities when carrying out tribochemical reactions. Identical features are identified by the same reference symbols. 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 cannot damage the movement devices in a corrosive or other way. In this case, the higher load must be taken into account when designing the movement device 5.
Die gemahlenen Erze/Mineralien werden auf einem in lotrechter Richtung im Schwerefeld auf- und abschwingenden Teller in einen Zustand gebracht, bei dem die granuläre Schüttung sich ähnlich einer flüssigen Phase verhält, die aus festen Bestandteilen besteht. Dabei bilden sich an der Grenzfläche dieser flüssigen, granulären 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 granuläre Teilchen aufeinander, dann können die im Reaktionsraum befindlichen Gase tribochemisch an den Stoßstellen katalytisch miteinander reagieren. Werden beispielsweise Titanerze, Ti- tanmineralien aufbereitet wird Titan/Titanoxid als Endprodukt angestrebt. 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 ground ores / minerals are brought into a state on a plate which swings up and down in the vertical direction in the gravitational field, in which the granular bed behaves similarly to a liquid phase which consists of solid components. At the interface of this liquid, granular layer with the (protective) gas phase, Faraday instabilities form, for example in the form of spatially stable wave patterns. Inert gases, preferably noble gases, preferably argon and helium, are preferably used as the protective gas. If individual granular particles collide in the particularly excited areas of this layer, the gases in the reaction space can react catalytically with one another tribochemically at the joints. If, for example, titanium ores and titanium minerals are processed, titanium / titanium oxide will be the end product. 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 vaporizes as a gas.
Soll beispielsweise im Fall des Titantetrachlorids daraus direkt Titandioxid hergestellt wer- den, kann das Sublimat bei hoher Temperatur mit Sauerstoff vermengt und zu Titandioxid oxidiert werden. Das hierbei entstehende Chlorgas kann in den Prozeß zurückgeführt werden.For example, if titanium dioxide is to be produced directly from titanium tetrachloride, the sublimate can be mixed with oxygen at high temperature and oxidized to titanium dioxide. The resulting chlorine gas can be returned 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 wer- den.If, in the case of titanium tetraiodide, metallic titanium is to be produced directly from it, the sublimate / steam is decomposed, for example on electrically heated tungsten wires, at approximately 1300 ° C to form compact titanium and iodine. The iodine can in turn be returned to 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 explained 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 reaction, a metal salt or. created a complex. This metal salt / complex can then be processed further. Solutions of several metal salts can be separated here, for example, using a method which is described in the international patent application PCT / DE02 / 01377.
Beispielsweise eignet sich das beschriebene Verfahren, wie oben erläutert, auch zur Gewinnung von (Roh-)Titan und Titandioxid aus den bekannten titanhaltigen Mineralien, beispiels- weise 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 the extraction of (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. If chlorine or iodine is advantageously used as 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 a titanium sponge. However, the titanium tetraiodide is sublimed and the pure titanium is deposited therefrom with thermal decomposition, without the formation of sponges.
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 above description, the claims and the drawing can be used both individually and in any combination for the Realization of the invention in its various embodiments may be of importance.

Claims

Ansprüche Expectations
1. Verfahren zum Durchführen einer tribochemischen Reaktion, dadurch g e k enn z e i c hn e t, daß Faraday-Instabilitäten erzeugt werden, indem ein granuläres, körniges oder aus Kugeln gebildetes Medium räumlich hin und her bewegt wird, wobei mit Hilfe der Faraday-Instabilitäten an Kontaktstellen/-punkten von Partikeln des Mediums tribochemische Reaktionsbedingungen gebildet werden.1. A method for carrying out a tribochemical reaction, characterized in that Faraday instabilities are generated by spatially moving a granular, granular or spherical medium, the Faraday instabilities at contact points / -points of particles of the medium tribochemical reaction conditions are formed.
2. Verfahren nach Anspruch 1 , dadurch g ek ennz e i chn et, daß nicht an der Reaktion teilnehmende Formkörper, insbesondere Kugeln, als Medium zur Durchfuhrung der Reaktion verwendet werden.2. The method according to claim 1, characterized g ek ennz e i chn et that molded bodies not participating in the reaction, in particular balls, are used as a medium for carrying out the reaction.
3. Verfahren nach Anspruch 1 oder 2, dadurch g ek ennz ei chnet, daß inerte Metallkugeln, insbesondere Edelstahlkugeln verwendet werden.3. The method according to claim 1 or 2, characterized g ek ennz ei chnet that inert metal balls, in particular stainless steel balls are used.
4. Verfahren nach Anspruch 1 , dadurch g ekennz e i chn e t, daß selbst an der Reaktion beteiligte Medien, insbesondere Erze, als Medien zur Durchführung der Reaktion verwendet werden.4. The method according to claim 1, characterized g ekennz e i chn e t that even media involved in the reaction, in particular ores, are used as media for carrying out the reaction.
5. Verwendung eines Verfahrens nach einem der Ansprüche 1 bis 4 zur kohlefreien Herstellung von Metall und Metalloxid.5. Use of a method according to one of claims 1 to 4 for the carbon-free production of metal and metal oxide.
6. Verwendung eines Verfahrens nach einem der Ansprüche 1 bis 4 zur kohlefreien Herstellung von Titan und Titandioxid.6. Use of a method according to one of claims 1 to 4 for the carbon-free production of titanium and titanium dioxide.
7. Verwendung eines Verfahrens nach einem der Ansprüche 1 bis 4 zur kohlefreien Her- Stellung von Metallkomplexen.7. Use of a method according to one of claims 1 to 4 for the carbon-free production of metal complexes.
8. Verwendung des Verfahrens nach einem der Ansprüche 1 oder 4 zur kohlefreien Herstellung eines Metalls und eines Metalloxids, wobei einzelne Fraktionen des aus dem Erz erzeugten Materials abgetrennt werden, um daraus ein Metall, ein Metallsalz oder ein Metalloxid zu erzeugen. Vorrichtung zum Durchführen eines Verfahrens nach einem der Ansprüche 1 bis 4 mit einem umgebenen Reaktionsraum, in dem eine Auflagefläche für ein granuläres, körniges oder aus Kugeln gebildetes Medium gebildet ist, wobei die Auflagefläche an eine Bewegungseinrichtung gekoppelt ist, mit der das granuläre, körnige oder aus Kugeln gebildete Medium zum Erzeugen von Faraday-Instabilitäten an Partikeln des Mediums für eine tribochmische Reaktion hin und her bewegt werden kann. 8. Use of the method according to one of claims 1 or 4 for the carbon-free production of a metal and a metal oxide, wherein individual fractions of the material produced from the ore are separated off in order to produce a metal, a metal salt or a metal oxide therefrom. Apparatus for carrying out a method according to one of claims 1 to 4 with a surrounding reaction space in which a support surface for a granular, granular or spherical medium is formed, the support surface being coupled to a movement device with which the granular, granular or medium formed from spheres for generating Faraday instabilities on particles of the medium can be moved back and forth for a tribochemical reaction.
EP03773570A 2002-10-22 2003-10-22 Method and device for carrying out a tribochemical reaction Expired - Lifetime EP1558774B1 (en)

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