DE1442758A1 - Process for the production of an oxide of one of the elements titanium, zirconium, iron, aluminum and silicon - Google Patents

Description

Laporte Titanium Limited, London (Great Britain)

Process for the production of an oxide of one of the elements titanium, zirconium, iron, aluminum and silicon.

The invention relates to the production of oxides of the elements titanium, zirconium, iron, aluminum and Silicon through the oxidation of chlorides of these elements,

It has already been suggested to put titanium dioxide through it produce that titanium tetrachloride is reacted with oxygen in the vapor phase, but have thereby Difficulties arise because at least a portion of the titanium dioxide forms as a deposit on reactor surfaces seeks contact by the hot mixture of reactants or the hot mixture produced during the reaction Titanium dioxide or both.

This titanium dioxide deposition presents a serious problem for several reasons.

First is the deposited titanium dioxide

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not in finely divided pigment-like form, and if, as is usually the case, pigment-like titanium dioxide is to be produced, the formation of the deposited non-pigmentary titanium dioxide the overall effectiveness of the procedure "

Second, it can build up deposited titanium dioxide require frequent interruptions in the process to remove the deposited material before proceeding a blockage occurs. The risk of a blockage is especially large when the build-up of deposited titanium dioxide occurs in the region of a gas inlet through which through one of the reactants into the reaction chamber is introduced, ■

Third, if the wall of the reaction chamber is made of a refractory material such as silica, even a thin layer of deposited Titanium dioxide cause that in the wall of the reaction chamber as a result of various types of contraction during cooling cracks appear in the reactor. Similar considerations apply when attempting the others above To produce oxides by such a process.

The earlier proposals for creating pigment-like Titanium dioxide from the vapor phase oxidation of titanium tetrachloride can In two fundamentally different ways to be subdivided by procedures. '

In procedures of the first kind, usually called burning

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ner process ^ are designated, the reacting gases are converted into a _; empty reaction chamber introduced, and there will be frequent. Measures taken for the purpose of ensuring, as far as possible, that the reaction takes place in a Zpneι., Which is remote from any reactor surface, and that the titanium dioxide produced does not come into contact with hot reactor surfaces.

In the case of procedures of the second kind, one essential newer development will represent the reaction in one fluidized bed of refractory particles carried out. Probably because of the abrasive action of the fluidized Bed-forming particles represent the deposit of titanium dioxide. the. Walls of the reactor a less serious problem than in the case of the Brenner process, however, if (as is often desired) the titanium tetrachloride is preheated, severe build-up will occur around the titanium tetra-chloride inlets.

The invention provides a method of manufacture of an oxydes etoea of the elements titanium, zircon, iron, aluminum and silicon by reacting a chloride of the element with an »oxidizing gas in the vapor phase, and this method consists in that the chloride and the oxidizing gas be pre-heated to such an extent that that if they were mixed together without a reaction et & ttfindefc, the temperature of the resulting Gemisöheg would be at least 70 ° G that the previous

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heated chloride vapor and the preheated oxidizing one. gas are introduced into a reaction chamber through separate inlet devices in such a way that a a whirling stream of intimately mixed gases is produced, in which the oxide is formed in finely divided form, that is an inert, particulate refractory material into the Reaction chamber is introduced in such a way that it impinges on the reactor surface or surfaces. , which are immediately adjacent to the gas inlet devices and are accessible to the two reactants, in order to prevent or considerably reduce the deposition of generated oxide on the surface or surfaces, that the particulate refractory material at least substantially from the reaction chamber in suspension in the swirling Gas stream is led out and that thereafter the particulate material is separated from the oxide produced.

A particularly important embodiment of the process is the one in which the oxide produced is pigment-like Titanium dioxide and the chloride is titanium tetrachloride.

The process can be carried out in a reactor of the fluidized Bed working type, or by burner type. .

The reason why the inert particulate refractory material impacted on the said Areas the deposition of generated oxide on this surface chen considerably diminishes is not; .completely clarified,

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especially since in the pall of titanium dioxide the layer of deposited Titanium dioxide is harder than silica, and is still due to the introduction of inert particulate Material in a manner that does not noticeably wear the silica walls of a reaction chamber or of a gas inlet pipe causes a considerable reduction in the deposition of titanium dioxide on the walls brought about.

If an old fluidized bed operating reactor is used, the fluidization as such creates sufficient swirling conditions to ensure good mixing of the reactants. However, when a burner type reactor is used, it is essential that the plus velocity of the gas mixture within the oxidation zone correspond to a Reynolds Flow Number of at least 10,000 and preferably of at least 20,000. If, in a reactor of the burner type, the reactants (as described below!) Are introduced through parallel inlets (especially non-coaxial parallel inlets), the plus velocity of the gas mixture within the oxidation zone preferably corresponds to a Reynold flow number of at least 50,000.

The inert, particulate refractory material must be a hard solid which is essentially not attacked at the elevated temperature and under the other conditions obtained during the reaction

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Material may for example consist of zirconium particles or alumina particles or titanium dioxide particles withdrawn from a fluidized bed of titanium dioxide particles as used in a process for the manufacture of titanium dioxide by the vapor phase oxidation of titanium tetrachloride within the bed. The material expediently consists of silica sand. The material = can also be a mixture of more than one of these or other materials. Essentially all of the particles can be of a size equivalent to a +85 "mesh BSS sieve. The practical upper limit on particle size is generally determined by the requirement that the particulate refractory material be carried out of the reaction chamber by the gas stream. Preferably essentially all particles are of sizes within the range of -8 to +30 BSS mesh.

The optimal rate of introduction of the inert, particulate refractory material depends on the The design and dimensions of the reactor depend on and can be changed while the process is being carried out. Palis the speed is high, the amount of material to be separated from the oxide produced is correspondingly large, and when (as will be described below) the material is cold in a stream of carrier gas into the reaction chamber is introduced, excessive cooling of the reac-

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tion partner with a resulting incomplete Dictionary a, ufenken.

The inert, particulate refractory material should enter the reaction chamber at a rate of at least 23. m / sec, preferably at least 20 m / sec inserted, will. The upper limit of the rate of introduction ^ of the -inert, particulate refractory material is determined by that requirement that the velocity should not be so high that excessive wear of the surface or surfaces of the reactor is caused. In general should the. The rate of introduction of the particulate refractory material must not be greater than about 91 to 122 m / sec.

Advantageously, the inert, particulate refractory material enters the reaction chamber at a temperature introduced, which is considerably below the temperatures at which the preheated oxidizing gas and the preheated chloride can be introduced into the reaction chamber. There are two reasons for this.

First, especially if the reactor surface or surfaces are not themselves indirectly cooled by the use of a coolant which does not come into contact with the reactants (as described below), the deposition of oxide produced on such surface or & vt £ can such surfaces cannot be effectively reduced or prevented unless the particulate fire

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solid material, -immediately before it on this surface or this area occurs, is at a temperature that is significantly lower than the temperatures with which the preheated reactants in the reaction chamber to be introduced.

Second, if the particulate refractory material reaches too high a temperature (more than about 90 ° C, if the oxide generated is titanium dioxide) before it leaves the reaction chamber, oxide generated on the particulate refractory material can be deposited to an undesirable extent.

On the other hand, it is important that the reactants are not excessively cooled by the introduction of the particulate refractory material. Further, if the particulate refractory material is one that has been returned to the process after separation from the oxide produced, some unreacted chloride (particularly if the efficiency of the reaction is considerably less than TOO $) may be absorbed on the material . The material should then not be cooled below the dew point of the chloride (ie the material should not be cooled below a temperature of about 150 ⁰ C if the chloride consists of titanium tetrachloride, the dew point of which is 156 ⁰ C at atmospheric pressure) before it is reintroduced into the reaction chamber, "-. ·· The particulate refractory material can be re-introduced into the re-

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Action chamber in suspension in one or in both of the preheated reactants and / or in suspension in an inert protective gas (barrier gas) which (as will be described below) can be introduced into the reaction chamber. Optionally, at least a portion (preferably all) of the particulate refractory material can be introduced into the reaction chamber in suspension in one or more streams of carrier gas through inlet devices separated from the inlet devices for the preheated reactants , the carrier gas preferably so is directed such that it causes the particulate refractory material to impinge directly on the reactor surface or surfaces on which the gas inlet means immediately adjacent and are open to both reactants.

When the particulate refractory material is introduced into the reaction chamber in suspension in either or both of the preheated reactants, it is usually preferable to introduce the material in suspension in the preheated oxidizing gas. Some form of seal must be provided to prevent gas from entering the particulate refractory feed system, and it is easier to provide such a seal for the preheated oxidizing gas than for the preheated chloride, which is corrosive . Similar considerations can arise if the particulate fire

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solid material in a protective gas is introduced when this consists of chlorine, and also (as will be described below) the inert gas inlets are common much more restricted than the reactant inlets.

When the particulate refractory material is in the Reaction chamber in suspension in one or both of the Preheated reactants is introduced, it is preferably introduced into the reactant or reactants at one or the other introduced at several locations sufficiently close to the reactant inlet devices lie that the particulate refractory material in the reaction chamber with a temperature occurs which is considerably below the temperatures at which the preheated reactants enter the reaction chamber ..

In comparison to the use of a carrier gas, the introduction of the particulate refractory material brings in Suspension in one or both of the preheated reaction units. partner and / or in a protective gas with various advantages. Firstly, this will lead to the introduction of an additional, avoided gaseous component, which could excessively cool the reactants, which further slow down the reaction and would absorb some of the heat of reaction and which if the carrier gas does not consist of chlorine,. the chlorine produced in the reaction would dilute what would make the chlorine more difficult to extract

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is and less for the immediate return in a chlorinator is suitable. Second, it avoids the need for additional supply and inlet devices to be provided for a carrier gas, so that the design of the reactor can be simplified. Third this enables the particulate refractory material to be introduced where there is insufficient space is present to provide a carrier gas inlet (which normally has an inside diameter of at least 6 mm must have). In general, these considerations are of greater importance for smaller reactors.

When the particulate refractory material into the reaction chamber is introduced in suspension in a carrier gas, the carrier gas can be an inert gas (i.e. a gas that under the conditions of the reaction towards the reactants is inert), for example chlorine or nitrogen or (except when the carrier gas inlet is within a Chloride inlet) an oxidizing gas (preferably air) that has not been preheated like this is given here. Compared with the introduction of the particulate refractory material in suspension in one or both of the preheated reactants and / or The use of a carrier gas in protective gas has various advantages.

First, it is possible to use the flow or flows of carrier gas in such a way that essentially the entire particle

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shaped refractory material impinges directly on the reactor surface or surfaces which are immediately adjacent to the gas inlet devices and which are accessible to both reactants. In this way substantially all of the particulate refractory material is usefully used and it is possible to obtain adequate coverage ^; to provide the reactor surface or surfaces with a smaller amount of the particulate refractory material, which. means that less oxide produced is lost by deposition on the particulate refractory and that the separation of the particulate refractory from the oxide produced is facilitated.

Second, it enables the particulate

c refractory material in the reaction chamber with a tempe-; temperature to introduce which is considerably lower than the temperatures at which the preheated reactants are introduced into the reaction chamber. So that. A carrier gas into the reaction chamber can be introduced at a temperature not greater than 150 ⁰ C. In order to minimize the disadvantages associated with introducing a relatively cold carrier gas into the reaction chamber, the concentration of the particulate refractory material in the carrier gas should be high, for example about 3.2 kg per cubic meter of carrier gas. The advantages associated with the use of a carrier gas are generally of greater importance in large reactors and

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in reactors in which the inner surface of the reactor wall is not indirectly affected by the use of a coolant cooled (as described below).

When the particulate refractory material is introduced into the reaction chamber in suspension in a carrier gas the carrier gas can be introduced in a number of different ways depending on the design and type of the reactor depend.

In the case of a fluidized bed Reactor in which the chloride is introduced into the fluidized bed through one or more gas inlet lines which may lead to inlet openings which are flush with the inner surface of the side walls of the reactor a flow of the carrier gas containing the suspended particulate refractory material into or into each of these Gas inlet lines are introduced at a short distance from the inlet opening, the flow being so shaped and / or is directed to impinge on the wall of the conduit over its entire end portion. So can he or everyone Stream of the carrier gas through a nozzle hinduroh are introduced coaxially within a chloride inlet line is arranged at such a distance from the open end of the conduit that the conical one emerging from the nozzle Jet of suspended particulate refractory material directly onto the wall of the end portion of the conduit hits. Instead, the or each stream of the

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Carrier gas in a chloride inlet pipe in tangential Direction and either perpendicular to the axis of the line or directed so that the current has a movement coraponent in the direction of flow of the chloride along the conduit.

In the case of a burner type reactor in which the reaction chamber is generally cylindrical, one the reactant (preferably the chloride) into the reaction chamber introduced through one or more inlet openings in the side wall of the reaction chamber, and the other reactant (preferably the oxidizing gas) is introduced into the reaction chamber at an upstream point this inlet opening ouer openings is introduced, while the carrier gas containing the particulate refractory material in suspension enters the reaction chamber can be introduced through a nozzle located coaxially within the chamber and upstream the inlet opening or openings in the side wall of the Chamber lies so that the conical jet of suspended particulate refractory material exiting the nozzle impinges directly on the reactor surfaces that the inlet opening or the inlet openings in the side wall of the reactor are adjacent "

In the case of a burner type reactor in which the Chloride and the oxidizing gas can be introduced through inlets which are coaxial with one another

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carrier gas containing the particulate refractory material is introduced through an inlet located within the inner inlet conduit and so arranged is that it casts a conical jet of suspended particle-shaped refractory material onto the inner surface of the end part of the inner inlet conduit. Instead of this the carrier gas can also be introduced through an annular inlet which has an inlet for the Chloride or the oxidizing gas surrounds and so arranged is that it 'directs a converging stream of suspended particles onto the reactor surface which is this inlet for the chloride or the oxidizing gas immediately surrounding it.

Further, these two assemblies may be combined, so that the particulate refractory material is caused to directly impinge on both the inner and the outer surface of the Ehdteiles a reactant inlet line. When the chloride inlet forms the innermost of two or more coaxial inlets, a conical jet of suspended particulate material can be caused to impinge immediately on the inner surface of the end portion of the chloride inlet conduit from an axially disposed carrier gas nozzle and at the same time particulate refractory material can be caused to hit the Outer surface of the end part of the chloride inlet pipe to be hit by placing part of the material in the

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preheated oxidizing gas is suspended and the oxidizing gas enters the reaction chamber through an annular Inlet therethrough surrounding the chloride inlet. Numerous other variations are possible. So For example, the central carrier gas nozzle, which emits a conical jet of suspended particulate refractory Material supplies, can be replaced through a tangentially directed inlet, which is a spiral Electricity generated by the material.

In the case of a burner type reactor in which the chloride and oxidizing gas are passed through inlets are introduced whose axes are parallel to each other, but which are arranged next to each other and not one inside the other may be the suspended particulate refractory Material containing 'carrier gas are introduced through one or more inlets, which with their Axes are parallel to those of the reactant inlets and upstream of the latter. These The arrangement can, if desired, be supplemented by having further particulate refractory material in suspension in the preheated oxidizing gas.

If the design and dimensions of the reactor permit, any of the arrangements described above can be used for the introduction of the particulate refractory material through a movable nozzle for the partially

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Chen-shaped refractory material in suspension containing carrier gas can be replaced or supplemented. For example, a fixed nozzle which delivers a conical jet of suspended particulate refractory material can be replaced by a nozzle which delivers a stream of suspended particulate material and which is continuously rotated about an axis which is at an acute angle (e.g. half angle of the conical jet) is inclined with respect to the axis of the substantially cylindrical stream of suspended particulate refractory material. Instead, such a movable nozzle may be arranged for intermittent operation to supplement the fixed inlet device for the carrier gas, the arrangement being such that the nozzle can be moved to direct particulate refractory material at a location selected by an operator . So can a complementary stream of particulate! refractory material can be directed at one or more different locations at such time or times as observation or experience makes it appear necessary or desirable.

Preferably, the reactor surfaces that are generated for the mixed reactants and / or for the hot Oxide are accessible, indirectly cooled by using a coolant. The reactor area or areas that the

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Inlet device for the chloride and / or the inlet device for the oxidizing gas are adjacent, can can also be cooled indirectly using a coolant, as for example in the British patent 764 082 is described.

The cooling of the reactor surfaces is for several reasons cheap. First, the cooling of the surfaces as such seeks the deposition of generated oxide on the surfaces impede. Second, such generated oxide, which may be deposited on the cooled reactor surfaces, can be one have a softer shape than when deposited on uncooled reactor surfaces and this makes removal easier of such deposited oxide through the particulate refractory material, even in places spaced apart downstream of the region of introduction of the particulate refractory material into the reaction chamber. Third, due to the fact that the most important Heat transfer mechanism that controls the temperature of the particulate Refractory material in a burner process seeks to increase the conduction of heat from the reactor surfaces during the impact of the particles on the reactor surfaces is the maximum by cooling these surfaces Temperature reached by the particulate refractory material decreased. As mentioned above, it is It is advantageous that this material does not reach too high a temperature, because otherwise the oxide produced on the refractory parts

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Chen can be deposited to an undesirably high level. Fourth, the cooling of the reactor surfaces enables that at least a part of the reactor is made of metal instead of non-metallic refractory material, vfie silica, can be made, and as will be discussed below, this is often an advantage.

To all or part of the reactor made of metal instead of a non-metallic refractory material To be able to manufacture, a considerable degree of cooling is required, depending on the particular one used Metal depends. For example, must be in the pail of nickel the reactor surfaces are cooled to a temperature below 3> 25 ° C will. The lowest temperature to which the reactor surfaces can be cooled is (in the case of large reactors, at where there is no risk of premature deterrence of the reactants) determined by the dew point of the chloride. For example, if the chloride consists of titanium tetrachloride, the reactor surface must not be at one temperature be cooled below 140 ° C.

On the other hand, it has been found that if the cooled reactor surface is made of a non-metallic refractory Material is made, even a relatively small degree of cooling is beneficial, especially for those parts the area which is a considerable distance downstream of the reactant inlet devices, and if that oxidizing gas is present in excess of the amount that

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it is necessary to react with the chloride in a stoichiometric ratio. Thus, it is advantageous if the reaction temperature is within the range of 1000 ° to 1300 ⁰ C to cool the reactor surfaces to a temperature below 900 ⁰ C, advantageously below 800 ° C and preferably in such that a value of 650 ⁰ C does not exceed. The coolant can be water, steam, oil, a molten metal salt or a molten mixture of metal salts (for example, a mixture consisting of 4.0 % sodium nitrite, 7 % sodium nitrate and 53 % potassium nitrate, based on the weight of the mixture, and having a melting point of 141.2 ° C), which depends on the material from which the reactor or the part of the reactor to be cooled is made. If this material is a metal \

in general, any of the coolants mentioned can be used. However, when the material is a non-metallic refractory material, only certain molten metal salts or certain molten mixtures of metal salts can generally be used. \

Although it is necessary for the reasons mentioned above

is desired to cool the reactor surfaces that the reaction partners and are exposed to the hot generated oxide, care must be taken in the case of a burner process that the mixture of reactants is not cooled below the minimum satisfactory reaction temperature and the reaction is not deterred prematurely. Hence the

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Degree of cooling that can be used depending on the diameter of the reactor, with larger diameters allowing greater degrees of cooling, and it is therefore advantageous a reactor of sufficiently large internal diameter (expediently at least 10 cm and preferably of at least 15 era) to use indirect cooling to enable the reactor surfaces.

If the process is carried out using a fluidized bed, the degree of cooling should be not be so large that the fluidized bed is cooled below the minimum satisfactory reaction temperature will. If the oxidation of titanium tetrachloride is carried out by combining it with an oxidizing gas fluidized bed is implemented (with the titanium tetrachloride is not preheated), it is usually found that with a well thermally insulated reactor the heat losses from the reactor substantially offset the heat released by the reaction if the inside diameter of the reactor is about 38 cm. When the response is in a reactor of this diameter is carried out using titanium tetrachloride raised to a temperature of e.g. 800 ° C is preheated, then a certain degree of cooling of the reactor surfaces is possible. However, it is advantageous to use a reactor of larger diameter and / or heat by burning a gaseous Fuel, such as carbon monoxide, within the fluid

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to feed the discrete bed. However, special precautions must be taken to ensure that the combustion of the gaseous fuel is not considered this leads to a deposition of titanium dioxide on reactor surfaces which surround the fuel gas inlet (s).

Such precautions are shown in British Patent 37999/59 which describes a process for the preparation of titanium dioxide by oxidizing a titanium tetrahalide in the vapor phase by causing an oxidizing gas to react with the titanium tetrahalide in the presence of a fluidized bed called the particle having, in which at least part of the surface consists of titanium dioxide and which are at a temperature within the range of 800 ° to 1500 ⁰ C, wherein the oxidizing gas is introduced into the bed in an amount in excess of that in this method, which is required to react with the titanium tetrahalide, furthermore, carbon monoxide is introduced into the fluidized bed to react with the excess oxidizing gas, and the concentration of carbon monoxide in the zone of its introduction into the bed is reduced by introducing into the carbon monoxide introduced a diluent gas which consists of one of the gases nitrogen, chlorine and carbon dioxide or a mixture of several of these gases, the amounts of carbon monoxide and diluent gas being such that the volume

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moderate proportion of the diluent gas, based on the total volume of carbon monoxide and diluent gas, is within the range of 11 to 65 % . The diluent gas is preferably introduced into the carbon monoxide before the carbon monoxide is introduced into the fluidized bed. Similar considerations also apply if the chloride consists of perrichloride or silicon tetrachloride.

The correct choice of material for the construction of the reaction chamber walls and reactant inlet devices is important. Any reactor area that is not through a coolant is indirectly cooled and exposed to the hot chloride or chlorine or the hot generated oxide must be made of a non-metallic refractory material such as silica or alumina will. In the case of the reaction chamber walls, either the entire wall can be made of a non-metallic, heat-resistant material or the wall can be made of an outer shell made of a suitable metal which is provided with a lining made of a non-metallic heat-resistant material. Of the two above named non-metallic refractory materials, alumina has certain advantages over silica for Parts that are exposed to very high temperatures, however, parts of complicated shape can more easily be made from silica so this material is generally preferable.

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If desired, a non-metallic heat-resistant Material for part of the reactor and a different non-metallic refractory material used for another part of the reactor. Reactor surfaces, which are cooled indirectly with the aid of a coolant, if the degree of cooling is sufficiently large is made of an appropriate corrosion-resistant metal, . Such as nickel or a nickel alloy, and with a suitable design of the reactor can include the entire reaction chamber and inlet devices for the reaction partners made of metal will.

As a further precautionary measure to prevent or reduce the deposition of generated oxide on reactor surfaces which are adjacent to the inlet devices for the reactants, at least one reactant inlet can be surrounded by a protective gas inlet and / or separated by a protective gas inlet from another reactant inlet or the inner surface of the reaction chamber wall , whereby a protective gas which is inert towards both reactants, preferably chlorine, which is generated during the reaction, or nitrogen or another inert gas, is introduced into the reaction chamber through the protective gas inlet «. The protective gas is preferably introduced into the reaction chamber at a temperature of at least 150 ° C, and the speed of the protective gas immediately

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directly before eg is introduced into the reaction chamber is at least 30 m / sea (preferably about 90 m / sec). Around * to prevent excessive cooling of the reactants, especially if a small reactor is used the protective gas is preferably preheated to a temperature within the range of 600 ° to 100 ° C.

Although the gases are in a swirling state within the reaction chamber, the protective gas is too prevent one reaction partner from coming into contact with the other while the first reaction partner is still is in contact with the inlet through which it is introduced into the reactor. For example, this can be Chloride in a stream of oxidizing gas flowing inside the reaction chamber (which is either one of the burner type or of of the fluidized bed type) flows, be inserted through an inner tube that is either flush with the inner surface of the reaction chamber wall end or (in the case of a burner reactor) into the speech ionskararaer can extend, and an inert protective gas can introduced into the reaction caaaaer through an outer tube which is arranged coaxially with the inner tube and ends flush with the end of the inner tube.

With a suitable choice of flow velocities for the protective gas and the chloride, and if care is taken, the wall thickness of the inner tube is not too great 1st, the protective gas prevents the chloride world-wide from entering

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To come into contact with the oxidizing gas in a zone which is immediately adjacent to the annular end face of the inner tube, because the ^x s chloride and the protective gas together reduce the concentration of the oxidizing gas at this surface considerably. Nevertheless, the introduction of a protective gas around an inlet for one reactant is not to be viewed in such a way that the reactor surfaces which are adjacent to this inlet are inaccessible to the other reactant. Therefore, the introduction of a protective gas is in addition to and does not replace the introduction of the particulate refractory material.

If a burner type reactor is used, then the introduction of a protective gas in connection with numerous arrangements of the inlet devices for the reactants to be used. So when the preheated chloride and the preheated oxidizing gas enter the reaction chamber through an inner and an outer inlet which are coaxial with one another, the protective gas is preferably introduced introduced through a third coaxial inlet located between the inner and outer reactant inlets. The protective gas can also by a annular inlet through which surrounds the outer of the two inlets for the reactants. When the preheated oxidizing gas and the preheated Chloride is introduced into the reaction chamber through inlets

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that are not arranged one inside the other, but rather run parallel or obliquely to one another, then the protective gas can pass into the reaction chamber through inlets are introduced, each of which has one of the inlets for the reactants surrounds, or the protective gas can only be introduced around one or some of the inlets for the reaction partners will. When the oxidizing gas is caused to flow along the reaction chamber and when the chloride introduced into the stream of oxidizing gas through a slot provided in the wall of the reaction chamber the chloride can first be supplied through an outer slot which is narrower than the slot is in the wall of the reaction chamber to form a ribbon-shaped stream of the chloride and the protective gas can enter the reaction chamber is inserted through the inner slot on both sides of the ribbon-shaped chloride stream will.

When a burner type reactor is used, the movement of the particulate refractory material be supported through the reaction chamber by arranging the reaction chamber with its axis perpendicular and making the gas flow pass through them near the bottom · If a fluidized bed operating reactor is used, the size of the inert refractory particles that are caused to act on the Reactor surface or surfaces to meet the size fler

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Particles forming the fluidized bed and to the Velocity of the fluidizing gas in such relation that despite the inhibiting influence of the the particles forming the fluidized bed, the first-mentioned particles essentially in the gas stream exiting the bed get picked up.

The invention also provides a modification of the "method described above, in which the reaction in a fluidized bed and the inert particulate refractory material. remains in the fluidized bed and forms part of it. Preferably consist the fluidized bed particles and the inert refractory particles of the same material. The added ones Oxide particles can be obtained from another fluidized bed process for the oxidation of the Chlorides can be obtained, or they can be obtained from the fluidized bed of the present Process particles are withdrawn, whereby the withdrawn particles can be milled before they leave the bed can be added. In this way, the addition of the oxide particles for the purpose of reducing or preventing the deposition of generated oxide on reactor surfaces also serve to the size distribution of those making up the fluidized bed To regulate particles, as in the UK patent 866 565 is shown, which is a method of manufacturing of titanium dioxide by oxidation of a titanium tetrahalide

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describes in the vapor phase, wherein the reaction between the Titantetrahalogeniddampf and oxygen or an oxygen-containing gas within a bed of particles of a refractory material occurs, which is maintained in a fluidized state at a temperature within the range of 750 ° to 1500 ⁰ C, wherein at least some of the titanium dioxide remains in the bed and the size distribution of the particles forming the bed is controlled by gradually adding fluidizable particles of alumina, silica, zirconia, zirconium or titanium dioxide or a mixture of some or all of such particles to the bed from an external source and particles are gradually withdrawn from the bed, the mean size of the added particles being smaller than the mean size of the withdrawn particles. This operation compensates for the growth of the bed particles resulting from the deposition of generated oxide on these particles.

If the inert, particulate refractory material is retained in the fluidized bed, material must be removed from the fluidized bed to prevent the bed from increasing indefinitely. The removed material can be used for some other purpose . For example, titanium dioxide obtained in this way can be used in the manufacture of ceramic materials , or it can be at least partially chlorinated

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(preferably using the chlorine formed as a by-product in the oxidation reaction) and the resulting chloride and any oxide particles of reduced size can be recycled to the fluidized bed. This procedure is shown in British patent 6393/60, which describes a process for the production of an oxide of one of the elements titanium, zirconium, iron, aluminum and silicon by reacting a chloride of the element with an oxidizing gas in the vapor phase, in which the reaction is carried out within a bed of particles of the oxide of the elements mentioned or a mixture of oxides of more than one of said elements, the bed is maintained in a fluidizing state at a temperature within the range of 750 ° to 1500 ⁰ C, a portion of of the generated oxide is left in the bed and the size distribution of the oxide particles forming the bed is regulated by withdrawing oxide particles from the oxidation zone, reacting the withdrawn particles with a chlorinating and reducing agent in order to reduce their size and form the chloride, and Particles of reduced size from the chlorinator ungazone are removed by allowing them to be entrained in the gas stream leaving the chlorination zone as a result of their reduction in size, and the reduced size oxide particles and the chloride vapor entering the oxidation zone

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be guided.

The oxide produced is suitably different from the inert particulate Refractory material separated using a settling chamber, however, can also be dry or wet Cyclones can be used either in place of or following the settling chamber; After the inert particulate Refractory material has been separated from the oxide produced, it is preferably cooled and then returned to the reaction chamber.

It is important that the design of the reactor, the temperatures and the flow rates of the reactants are such that the reactants and the products the reaction in the oxidation zone for a period of time remain, which is long enough to ensure an essentially complete implementation, but which is not so long as to cause undesirable growth of the generated oxide particles. Usually see Residence times within the range of 0.02 to 10 seconds have all been found suitable. When the oxidizing gas from im consists of essentially pure oxygen or oxygen-enriched air, but then the residence time can as short as 0.01 seconds under appropriate conditions aein. When the gaseous reaction products with the Oxide in suspension generated the oxidation zone they are preferably subjected to a treatment for their rapid cooling or quenching to a temperature

909811/1028

- ye. -

below 90O ⁰ C (preferably below 65O ⁰ C) throws. This quenching of the reaction products can occur within the range of 0.01 to 10 seconds (preferably 0.05 to 5 seconds) from the time the chloride is introduced into the oxidation zone. The quenching can be effected in that cooled product gas, for example chlorine, is mixed with the product gas stream, which contains the generated oxide in suspension, or that the products are passed through cooled pipes at high speed. Suitably the quenching is effected by dispersing in the product gas stream a cold inert particulate refractory material which is preferably the same as the particulate refractory material used to prevent or reduce the deposition of oxide produced on reactor surfaces. Advantageously, the inert particulate refractory material used for the quenching and the inert particulate refractory material introduced into the reaction chamber are carried upward from the product gas stream to a device which is used for separating the inert particulate refractory material from the gas stream and for cooling the separated inert particulate refractory material serves, part of which is then returned to the process under gravity in order to deter further reaction products, and part of which is returned to the reaction channels.

909811/1028

will lead.

Various embodiments of Devices which are suitable for carrying out the method according to the invention, using the drawing, for example explained in more detail.

Pig.'i is a schematic axial section through a fluidized bed reactor.

Figure 2 is a larger-scale schematic above Axial section through one of the halide inlet tubes of a modified embodiment of the reactor shown in FIG. 1.

Pig · 3 is a cross section on line A-A of FIG Fig. 2.

Fig. 4 is a schematic on an enlarged scale Axial section through one of the halide inlet tubes of a second modified embodiment of that shown in FIG Reactor.

Flg. FIG. 5 is a cross-section on line B-B of FIG. 4. FIG.

6 is a schematic axial section, on an enlarged scale, through one of the halide inlet tubes a third modified embodiment of that shown in FIG Reactor.

Flg. 7 is a sheared axial section through a

909811/1028

Burner type reactor with slot inlets for one of the, reaction partners. Fig. 8 is an enlarged scale schematic axial section through part of the reaction shown in Fig. 7 and shows a modified arrangement and design of the inlets for one reactant.

Pig. Figure 9 is a schematic axial section through a burner type reactor with a shielding gas inlet.

Fig. 10 is a schematic axial section of the in Fig. 9 and shows a modified arrangement for the introduction of the inert particulate refractory material.

Fig.11 is a schematic axial section through a Burner type reactor with parallel, non-coaxial inlet tubes for the reactants.

Figure 12 "is a cross-section along the line CC of Figure 11. -

Fig.1? is «in a schematic axial section through a reactor of the burner type with inlets for a protective gas and means for indirect cooling of the reaction chamber wall.

90981 t / 1028

Pig .. 14 is a cross-section on the line D-D of FIG.

Fig. 15 is a schematic axial section through the shown in Fig. 13 reactor and shows a modified arrangement of the inlets for the reactants.

Pig.16 is a cross-section on the line E-E of FIG.

FIGS. 17 to 23 are schematic axial sections of FIG

seven torch-type reactors, all with inlets for a protective gas and with means are provided for indirect cooling of the reaction chamber wall.

Pig.24 is a cross-section on the line F-F of Fig.23.

Fig.25 is an axial section through a modified one Embodiment of a tube for insertion of the inert particulate refractory material.

Fig.26 is an axial section through an embodiment of a device for quenching the Reaction products.

That shown in Fig. 1, with fluidized bed working reactor has a cylindrical reaction vessel on, which is arranged with its axis perpendicular and at a short distance above its bottom wall with a

ORIGINAL INSPECTED

9 0 9 811/10 2 8

«. ■ '. 'V-. TU27S-B

porous plate & is provided, which weighs "eeftiruber '""across the entire inner space of the reaction vessel. The bottom wall of the reaction vessel 1 is marked with" a zem ""'^; Provided central inlet, to which the oxidizing * gas can be fed "through" a line 3 »In a short distance above the * top of the porous plate 2, four circular inlet openings are provided in the side wall of the reaction vessel, through which the chloride can pass four pipes ^ is fed in. At a certain distance above the chloride inlet part an overflow opening is provided which leads into a downwardly inclined pipe 5 into which the solid fisilöhen from the fluidized bed can overflow ;, 's'ö' that the overflow opening is the height of the Top of the fluidized ^; A certain inert particulate, very fiery material is in suspension; introduced in a chloride, which ^; is fed through each of the tubes k ^{* r} '-

As from Figures 2 and j? = Apparent, can j'eäe's of the four supply pipes chloride ^ - see ver-S with a innerön'ftohr ^ be, that to the tube 4 extends coaxially and "may be introduced by passing an inert particulate .feuerfester ¹ solid der'in a ^; suitable carrier is taken along, which is not supposed to be an oxidizing substance lichen 'immediately out' at least the end part of the surfaces of the inlet openings in the side wall ¹ .

"'' I DU 11/1 §2 §.: ..:;: ^; sr: t. BAD ORfQINAL

of the reaction vessel 1 impinge.

The oxidizing gas passes through the pores of the porous plate 2 at a high speed, and thereby the upper surface of the porous plate 2 becomes open to the Inaccessible to chloride.

As illustrated in Figures 4 and 5, can instead of the axially arranged tubes 6 also arranged tangentially Pipes 7 are used. In this embodiment, the required speed component becomes the inert particles are supplied along the tubes 4 exclusively by the flow of chloride through the tubes 4, however, in the case of the in Flg. 6 reproduced modified embodiment the inert particles through tangential straightened tubes. 8 introduced, which are inclined so that the inert particles with velocity components which are directed along the tubes 4.

According to an example of suitable dimensions for the reactor shown in FIG. 1, the internal diameter of the reaction vessel JO cm, and the centers of the Chloride inlets can be 5 inches above the top surface of the porous Plate 2, while the center of the overflow opening is 45 cm above the upper surface of the porous plate 2 can. The inner diameter of the chloride supply pipes 4 can be 10 mm, but in the case of the one in the figures 2. and 3 reproduced modified embodiment, this dimension should be increased.

BATH

90 9811/102 8

Gewüns chtenf alls the reaction vessel may ate 1., A jacket may be provided, may be passed through a cooling means for an indirect cooling of the Innenf ¹ Ia- ..... before the sidewall of the reaction vessel ate s provide 1. When .. the side wall of the reaction vessel 1 through the use; . a coolant is cooled, then, must, the fluidized bed, additional heat can be .zugeführt as mentioned above, unless the inner diameter of the reaction vessel ässes 1 being significantly greater than JO to 38 cm "-, _, - ■ -.-

The porous plate 2 is only one example of a large number of gas distribution systems which are suitable for: supporting the underside of the bed and for distributing., The supply of oxidizing gas evenly over the horizontal extent of the fluidized bed. For example, the porous plate 2 can be replaced by a plate provided with holes, provided that, as is known, the arrangement is such that, in use, the pressure difference between the part of the reaction vessel under the plate (usually marked with " Windlesten ^ir ) and the zone immediately above the plate in the order of magnitude of the pressure drop at the; - = fluidized bed is or is greater than this pressure drop / is ο The mentioned pressure difference can be obtained by who. that holes of the required small diameter are used, or, more preferably, some form of constriction device is provided which is either in

909811/1028 .. "■ - MDORMINM.

the LÖehef is inserted or connected in series with them. For example, mouthpieces with an opening diameter smaller than the inner diameter of the holes can be arranged on the underside of the perforated plate in alignment with the holes or provided at the lower ends of "tubes which extend into or through the holes - the mouthpieces can be removable, -to enable cleaning or replacement or exchange for mouthpieces with a different opening diameter. Bubble caps or return-preventing devices or gas-permeable barriers.-.-. (or a ¹ continuous gas-permeable membrane ) are arranged to prevent solids from falling down through the holes in the plate, these devices being able to produce all or part of the required pressure drop,

Some :: of numerous satisfactory. Arrangements * in which a perforated plate is provided * are in British Patent 794,666, in US Patent 2,503,788 and in "Chemical Engineering Progress",. _; Volume 49, No. 1Oi page 529 reproduced. Another possible .Gas ^. distribution system for the oxidizing gas is dasjen, ige,., das sin; US Patent, 2 fj k, 661 _describes: jeiäoeh-sei: bemerkti that the chloride, immediately, in the ,,, Cluidisierte bed and not in the coarse bed ,, ine.rten part away on. which the fluidized bed in, the arrangement.

BAD ORfQINAL 90981 171Ö28: -V-:, ■

14427 & S

g§ Maß ά & Ψ named patent sftg§§titzfe i

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1 / θιϊ iesstfi tfatersöltg einggftiif ^^ wefd ^ ii «· ^:
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Ie i 10 versfeiien ig - t> dar eft äeri an iCöiilfflittei tifffiäüfi ge. let; Werdeneil feaSfii: ütir eiiig- iöäif'ektt Kteilffife df ί * -
before ¹ sex leäfctiönskämmer ^ # örzög§M§öi © ie
for the eiiieri reaction partner (vörgMgsw # ise
w & is eiiie Me'iirzaöl from see in ifegsfiötitting:
göhiit ^ gfiti äiif, - the fnit gieioKe ^ Äigtänd from one another; tlfn den Ifinfaiig Mf; ReactiDösliäifinier ' § arcfeeiraiiet ünQ are surrounded by © iiifffi Vefteiierfgttarn Jg / iß ie'ri eifi SöfiT 1 ^ füi »di # Züfüiir d§§ Reäktiönspartnirs iriilödeti. , μ ^

The Küfiiinäntei 1ö ends tänffjitffifeär stromal) jiem Ife-i rites 12 * in eiü # ffi köfgefi Itetafii; & tf * öinatif . '
i§t öle ReäktieiSsteMrntr "- § fffit

§Si1! / 1§IS

BATH

can be fed through tubes 14 therethrough.

A tube 15 which is arranged coaxially to the reaction chamber 9 is, 'extends a short distance through the wall which is the upstream end the reaction chamber 9 closes, and the arrangement is such that inert particulate refractory material, that is in suspension in a carrier gas through the tube 15 is supplied, emerges in a conical jet which immediately hits the inner surface of the reaction chamber and impinges between the slots 11. Because of the used The two diametrically opposite inlets for the second reactant are very high flow velocities inaccessible to the reactant introduced through the slots 11, and it is therefore not necessary to cause the inert particulate refractory material to hit the reactor surfaces meets, which are in the vicinity of the two diametrically opposite inlets.

According to an example of expedient dimensions for the reactor shown in FIG. 7, the reaction chamber 9 an inner diameter of 35 * 5 cm and a length of β m have, the inner diameter of the supply pipes 14 can be 15 cm and the axes of these tubes 14 may be at a distance of 23 cm from the upstream end wall the reaction chamber 9 lie. It can be twenty-five Slots 11 may be present, each of which is 30 cm long and

BATH 909811/1 & 28

3.2 mm wide, making a total area of 242 cm results. . -.

V / Ie illustrated in Figure 8, the slots 11 of the reactor according to FIG. 7 through a system of holes 16 to be replaced. In this embodiment the holes are arranged in five circumferentially extending rows, the most downstream row 15 holes and each of the other four rows contains 44 holes, so that there are 19I holes in total. If the Inner diameter of the reaction chamber 9 is 35 * 5 cm, each hole can have a diameter of 12.7 mmj and the circumferential distance between the centers of adjacent ones Holes of each of the four rows on the upstream End can be 50 mm. The measured in the axial direction The distance between the circles on which the centers of the holes in adjacent rows lie can be 75 mm.

Another suitable 'embodiment of a Halogenideinlaßvorrlchtung for use in the model shown in Fig. ¹ J reactor is such as this patent is described in British patent specification 757 703 with reference to FIG. 1 and in which the inlet for the one reactant (preferably the chloride) is in the form of a single, circumferentially extending slot. The embodiments described with reference to Figures 2 and 3 of British Patent 757,703 can also be used, but must

inert partially shaped refractory material in suspension in which other reaction partners are introduced, and it a modification of the two feed systems shown in Fig. 7 is necessary «

The burner type reactor shown in FIG. 9 has a cylindrical reaction chamber 17 which does not necessarily need to be arranged with its axis horizontally, as shown, and which is provided with a jacket 18 through which a coolant circulates can be., an indirect cooling be * inner surface of the reaction chamber provide 17 * In the side wall of the reaction chamber 17 is provided near its ströinäufwäftsseitigen end an inlet opening, which can be a reaction partner (preferably, the oxidizing ßäs) 'supplied via a feed tube 19 . Immediately before the confluence of the pipe. 19 into the reaction chamber 17, this is provided with an inlet, through which a suspension of an inert, particulate refractory material in a carrier gas can be introduced into the reaction partner from a tube 20 of smaller diameter *

Two tubes 21 and 22 that are coaxial with each other and are arranged to the reaction chamber 17, extend through the upstream end wall of the reactions chamber up and into the reaction chamber * 'up to a point which is at a certain distance downstream of the upstream end of the cooling jacket 18 is located.

909811/1021

The inner tube.21 serves as inlet means for the other Reaction partner (preferably the chloride). ·, "Uh-d -ein: protective gas is introduced from a feed tube 23 into the area of circular cross-section passing through the two tubes

21 and 22 is limited. The end portion 24 of the outer tube

22 is tapered to increase the speed of the protective gas before it enters the reaction chamber 17. The particulate refractory material is used in the former Reaction partner taken along and meets the Outer surface of the tube 22, the end portion of which is adjacent to the inlet for the other reactant, and '' on the Surface of the reaction chamber 17. '■

As an example of appropriate dimensions for the reactor shown in FIG. 9, the inside diameter of the reaction chamber 17 can be about 25 cm, the inside diameter of the feed pipe 1.9 about 15 cm and the inside diameter of the pipe 20 'which injects the particulate refractory material - about 5 "cm ., respectively. the two pipes 21 and 22 can be located in the reaction chamber 17 via a Entfferhung ^ ö to a location about of about 1.2-m> 3 m'jenseits of ^'7 upstream located end of the cooling jacket 18 e.rstrek - ^ '---'-'. keny "and the length of the cooling jacket 18 can be -about- 6 ^ 4 m · ■. The inner diameter of the inlet pipe 21 can be about 6.5 mm, and with the exception of the conical part 24, the inner diameter of the outer pipe 22 can be the outer diameter of the inner pipe 21 μm about 25 mm over— ■

90 9 84 17 102 8 '"- ^ - _BA0

1U2758

stride. The length of the conical part 24 of the outer Tube 22 can be about 50 mm, and at the ends of the Roiire 21 and 22 can be the inner diameter of the outer tube 22 exceed the outer diameter of the inner tube 21 by about 3.2 mm.

The design for introducing the particulate refractory Material in the reactor shown in Fig. 9 can be modified as shown in Fig. 10 shown according to which the particulate refractory material is fed through a pipe 25 to a pipe 26 which is equiaxed is located within the inlet tube 21 and into which a carrier gas through a tube 27 of smaller diameter can be injected. A conical ray of the particulate Refractory material suspended in the carrier gas exits tube 26, which briefly ends in front of the tube 21, so that the jet impinges directly on the inner surface of the end part of the inner tube 21. One reactant (preferably the chloride) is fed to tube 21 through a feed tube 28.

The reactor shown in Figures 11 and 12 of the Burner type has a cylindrical reaction chamber 29, which need not necessarily be arranged with its axis horizontally, as shown in FIG. 11 is. However, the end wall of the reaction chamber 29 extend In a direction parallel to the axis of the reaction chamber 29, twelve inlet tubes 30 for the one reactant

BAD ORfQINAL

9 0 9 8 11/10 2 8

(■ for example the oxidizing gas), twelve corresponding ones ■ Inlet pipes · 31 for the other reaction partner (for example the chloride) and nineteen inlet pipes 32 of smaller Diameter for the introduction of an inert particulate refractory material suspended in a carrier gas. ·

The inlet tubes 30 and 31 for the reaction partners end altogether in a plane perpendicular to the axis of the reaction chamber 29 , and the inlet tubes 32 end in a plane which is parallel to and upstream of the first-mentioned plane. The separation between these two Planes are selected relative to the separation between the axes of the tubes 30, 31 and 32 (FIG. 2) in connection with the arrangement of the various types of tubes 30/31 and 32 over the surface of the reaction chamber 29 in such a way that the conical jets of the inert particulate refractory material suspended in the carrier gas emerging from the inlet tubes 32 impinge directly on the outer surfaces of the end portions of the inlet tubes 30 and 31 for the reactants and on the adjacent part of the surface of the rare wall of the reaction chamber 29. As a result, the particulate matter hits refractory material on the surface of the wall of the reaction chamber 29 along its length downstream of the inlet pipes 3 0 and 31 for the reactants. If so desired, the reaction chamber 29 can be provided with a jacket through which a

909811/1028 BAD

Coolant is led to indirect cooling of the Make the inner surface of the side wall of the reaction elbow 29.

As an example of appropriate dimensions for the. Figures 11 and 12 shown reactor can the inner diameter of the reaction chamber 29 is about 46 cm, the inside diameter of the inlet tubes 30 and 3I for the reactants about 19 mm and the inner diameter of the Tubes 32 are approximately 6.4 mm. The distance ,, · which the separating the two levels mentioned from each other, can be 13.5 cm, and the axes of the inlet pipes 30,, 31 and 32 can be spaced approximately 10 cm from each other be, the axes of the inlet tubes 32 for the particulate refractory material at a distance of 'about 5.8 cm from the inlet pipes 30 and 31 for the reactants.

The reactor of the burner type shown in Figures TJ and 14 has a cylindrical reaction chamber 33, which need not necessarily be arranged with its axis horizontally, as shown in Fig. 13, and which is provided with a jacket 34 through through which a coolant can circulate to an indirect one. To carry out cooling of the inner surface of the reaction chamber 33 .. The end wall of the reaction chamber is provided with two rectangular slots, which, as shown in FIG. 14 ^; .. ■ extend parallel to each other. To one of the ₍ i3c; hlit-

BAD LOCAL

90981 1/1 02 8 ν "

Ze leads a pair of equiaxed lines 35 and 36, of which the inner line 35 is an inlet line for one of the reactants, and the area between the inner line 35 and the outer line 36 enables a protective gas surrounding the reactant to be introduced into the reaction chamber 33 * A corresponding pair of coaxial lines 37 and 38 are led to the other slot, of which the inner line 37 is an inlet line for the other reactant, and the area between the inner line 37 ^and the outer line 38 allows a Protective gas can be introduced into the ReaktIonskammer 33, which surrounds this reactant.

As can be seen from FIG. 13, the two pairs of coaxial lines 35 * 36 and 37 > 38 are arranged at an angle in such a way that the two reactants (chloride and oxidizing gas) within the reaction chamber 33 are directed towards one another. Inert particulate refractory material is introduced into the reaction chamber 33 through each of the slots, and this material is preferably carried along in the two reactants! however, it can also be fed either in addition to or instead of the material fed in suspended in a reactant in suspension in the stream of protective gas which surrounds this reactant.

As shown in Figures I5 and 16, can

9098 1 1 / 102-8

1U2758

the rectangular slot inlets and the associated pairs of coaxial ducts 35, 36 and 37, 38 dueh circular Inlets and associated pairs of coaxial tubes 39, 40 or 41, 42 are replaced.

The burner type reactor shown in Fig. 17 has a cylindrical reaction chamber 43 which is not necessarily to be arranged with its axis horizontally, as shown in the drawing, and the is provided with a jacket 44 through which a coolant can be passed to provide indirect cooling the inner surface of the reaction chamber 43 to make. That upstream end of the reactor is open, and a pipe 45, · the outer diameter of which is only slightly smaller than that Inner diameter of the reaction chamber 43 is, extends coaxially into the reaction chamber 43 to a point that is a short distance downstream of the upstream end of the cooling jacket 44. The tube 45 serves as an inlet for one reactant (preferably the oxidizing gas) and furthermore for the inert particulate refractory Material suspended in this reactant.

The area between the inner surface of the reaction chamber 43 and the outer surface of the tube 45 serves as an inlet for din shielding gas. Two pairs of coaxial tubes 46, 47 and 48, 49 lead to two diametrically opposite one another Admission in the side wall of the reaction chamber 43. The

909811/1028

inner tubes 46 and 48 serve as inlets for the other Reactant (preferably the chloride) in which further inert particulate refractory material is entrained can be. The area between the outer surface of the inner tube 46 or 48 of each pair and the inner surface of the Outer tube 47 or 49 of this pair serves as an inlet for a protective gas.

The burner type reactor shown in Fig. 18 is similar to that shown in Fig. 17 except that the upstream end portion of the reaction chamber 29 has a double cone shape so that it has a constriction or constriction 50 and tube 45 is accordingly shaped. Furthermore, the cooling jacket 44 does not extend as far upstream as the end of the tube 45 *

The burner type reactor shown in Fig. 19 has a cylindrical reaction chamber 51 which need not necessarily be disposed with its axis horizontal as shown in the drawing and which is provided with a jacket 52 through which a coolant is passed can be conducted in order to undertake indirect cooling of the inner surface of the reaction chamber 51. Three tubes 53 * 54 and 55, which are coaxial to one another and coaxial to the reaction chamber 51, extend into the reaction chamber 51 through its open upstream end. The end parts of the tubes 53 * 54 and 55 are conical, the innermost tube 53 being ^the smallest

009311/1028

Conicity and the outermost tube 55 has the largest conicity.

The two inner tubes 53 and 54 extend over the same distance into the reaction chamber 51 > However, the outermost tube 55 extends beyond the two inner tubes 53 and 5 ^. The innermost tube 53.d serves as an inlet for one of the reactants, preferably the chloride. The area between the innermost tube 53 and the tube 54 serves as an inlet for the introduction of protective gas. The area between the tube 54 and the outermost tube 55 serves as an inlet for the other reactant, preferably the oxidizing gas. The area between the outermost tube 55 and the wall of the reaction chamber 51 serves as an inlet for the introduction of further protective gas. An inert particulate refractory material is introduced into the reaction chamber 51 in suspension in the reactant which is fed between the tubes 5 4- and 55; it can also be introduced in suspension in the other reactant and / or in the protective gas.

The burner type reactor shown in FIG. 20 has a cylindrical reaction chamber 56 which is connected to their axis is not necessarily arranged horizontally needs to be, as shown in the drawing, and which is provided with a jacket 57 through which a Coolant can be passed through in order to provide indirect cooling of the inner surface of the reaction chamber 56

909811/1028

to take. Four tubes 58, 59, 60 and 61 that are equiaxed to one another and are arranged to the reaction chamber 56, lead to a circular opening in the upstream end wall of the reaction chamber 56. The innermost Tube 58 serves as an inlet for one of the reactants, preferably the chloride. The area between the innermost pipe 58 and the next pipe 59 serves as Einr leave for the introduction of a protective gas. The area between 'see the pipe 59 and the next outer pipe 60 is used as an inlet for the other reaction partner, preferably the oxidizing gas. The area between the tube 60 and the outermost tube 61 serves as an inlet for the introduction of further protective gas.

At a certain distance downstream of the end wall of the reaction chamber 56, two diametrically opposed circular openings are formed in the side wall of the chamber, and to each of these openings a set of four coaxially arranged tubes 62, 63, 64 and 65 lead, the axes of the tubes these two tube sets coincide. When these two tube sets are springy, the innermost tube 62 serves as an inlet for one of the reactants, preferably the chloride. The area between the innermost pipe 62 and the next pipe 6j serves as an inlet for introducing a protective gas. The area between the tube 65 and the next outer tube 64 serves as an inlet for the other reactant, preferably the oxidizing gas.

'909811/102 8

The area between the tube 64 and the outermost tube 65 serves as an inlet for the introduction of further protective gas. With respect to each of the three sets of equiaxed inlets the cross-sectional areas of the two protective gas inlets are approximately equal to each other and considerably smaller than the Cross-sectional areas of the inlets for the reactants. An inert particulate refractory material is introduced in suspension in the reactant, which is passed through the outer reactant inlet of each of the sets of equiaxed inlets is introduced, i.e. through the three annular inlets through which the oxidizing gas is preferentially fed. Additional particulate Refractory material can be in suspension in the reactant passing through the inner inlet for the reactant each of the sets of equiaxed inlets is fed and / or introduced in suspension in the carrier gas will.

The one in Pig. The reactor shown in Figure 20 can be modified by providing it with more than two sets of transverse inlets, each with its own set of four equiaxed tubes corresponding to tubes 62-65 associated with each of the two sets of transverse inlets shown in FIG with these sets spaced equidistantly around the circumference of the reaction chamber 56. For example, three such sets of transverse inlets could be spaced apart

909811/102 8 ^BAD

-54- 1442753

of 120 ° around the axis of the reaction chamber or four such Sets of transverse inlets may be provided at 90 ° intervals about the axis of the reaction chamber.

The burner type reactor shown in Fig. 21 has a cylindrical reaction chamber 66 which need not necessarily be arranged with its axis horizontal as shown in the drawing and which is provided with a jacket 6j through which a coolant is passed can be performed in order to carry out an indirect cooling of the inner surface of the reaction chamber 66 . Two tubes 68 and 69 extend through the open, upstream end of the reaction chamber 66, which are arranged coaxially to one another and to the reaction chamber 66 and which end at the upstream end of the cooling jacket 67.

The inner tube 68 serves as an inlet for one reactant, preferably the chloride, the area between the two tubes 68 and 69 serves as an inlet for a protective gas, and the area between the outer tube 69 and the inner surface of the reaction chamber 66 serves. as an inlet for the other reactant, preferably the oxidizing gas. The cross-sectional area of the protective gas inlet is considerably smaller than the cross-sectional area of each of the two inlets for the. Reaction partner. An inert particulate refractory material is introduced in suspension in the reactant, which is released by the external reaction

.909811 / 1028 BADOR ₁₆₁ NAL

partner inlet, i.e. through the area between the outer tube 69 and the inner surface of the reaction chamber 66. Additional inert particulate refractory Material can be in suspension in that reactant that is fed through the inner tube 68, and / or in Suspension are introduced in the protective gas.

The burner type reactor shown in Fig. 22 has a cylindrical reaction chamber 70 which is connected to their axis is not necessarily arranged horizontally needs to be as shown in the drawing, and which is provided with a jacket 7I through which a coolant can be passed through in order to undertake indirect cooling of the inner surface of the reaction chamber 70. Extending through the open upstream end of the reaction karamer 70 are three tubes 72, 75, and 74, which are arranged coaxially to one another and to the reaction chamber and which terminate at the upstream end of the cooling jacket 71.

The innermost tube 72 serves as an inlet for one Reactant, preferably the chloride. The area between the innermost pipe 72 and the next pipe 75 serves as an inlet for a protective gas. The area between the tube 73 and the outer tube 74 serves as an inlet for the other reactant, preferably the oxidizing one Gas, and the area between the outer tube 7 ^ and the inner surface of the reaction chamber 70 serves as an inlet

909811/1028 '

for further shielding gas. The cross-sectional area. each of the two inert gas inlets is considerably smaller than the cross-sectional area of each of the two inlets for the reac-honing participants. An inert particulate refractory material is introduced in suspension into the reactant which is fed through the outer reactant inlet, ie through the area between _{: the} pipes 73 and 74. Additional inert particulate refractory material can be in suspension in the reactant passing through the innermost tube 72 is fed, and / or in suspension in the protective gas are introduced. The burner type cactor shown in FIGS. 2J and 24 has a cylindrical reaction chamber which is constructed from two parts 75 and 76 which are separated from one another ^to form a circumferential slot 77. The reactor need not necessarily be arranged with its axis horizontally, as shown in the drawing. Two annular flanges 78 and 79 extend outwardly from parts 75 and 76, respectively, of the reaction chamber and are arranged at the same distance from the center of the slot 77 .. Between the two annular flanges 78 and 79 extend two inner cylindrical flanges 80 and 81 and a outer cylindrical flange 82 and cylindrical flanges 80, 81 and 82 are all coaxial with the reaction chamber. The two inner cylindrical flanges 80 and 81 are one

BATH ORIGINAL

809811/1028: -

other equal and separated from each other around a circumferential slot 83 to form the center line of which lies in the same plane as the center line of the circumferential slot 77 and which is narrower than slot 77.

The two annular flanges 78 and 79 and the cylindrical planes 8O, 81 and 82 together form a distributor space, that of one of the reactants, preferably the chloride, is fed through two tubes 84 which are in In the longitudinal direction in opposite directions with respect to the slot 83 are arranged offset. This reactant emerges from the slit 83 in the form of a ribbon The current flows out in the radial direction inwards through the wider slot 77 against the axis of the reaction chamber 75 * 76 flows. Each of the annular flanges 78 and 79 is provided at two diametrically opposite points with inlet openings through which a Inert gas from four tubes 85 is introduced into the area through the two annular flanges 78 and 79j the two inner cylindrical planes 80 and 81 and the reaction chamber 75 * 76 is limited. The shielding gas occurs through the slot 77 on either side of the ribbon-shaped stream of reactant emerging from the Slit 83 emerges into the reaction chamber and has so the endeavor to prevent this reactant comes into contact with the adjacent annular end surfaces of the parts 75, 76 of the reaction chamber.

BATH ORIGINAL

809811/1021

The other reactant, preferably the oxidizing gas, is introduced into the open upstream end of the upstream portion 75 of the reaction chamber. The downstream part J6 of the reaction chamber is surrounded by a jacket 86 up to a point which is immediately downstream of the two downstream protective gas supply pipes 85, through which a coolant can be passed in order to indirectly cool the inner surface of the downstream part of the reaction chamber 76 . An inert particulate refractory material is introduced in suspension into the reactant which is fed through the open upstream end of the reaction chamber.

According to FIG. 25, the tube I5 of the in-Fig. 7 shown Burner type reactor can be replaced by a tube, generally indicated at 87, and its end portion 88 has a reduced diameter compared to the main part 89. The parts 88 and 89 are through a conical part 90 connected to each other. For example Appropriate dimensions for the pipe 87, the inner diameter of the main part 89 can be about 5 cm, the inner diameter of the end portion 88 about 2.5 cm, and the length of the

approximately

End part 88 / 2.5 cm. The shape of the one shown in FIG Tube can (with appropriate choice of dimensions) also for the drill 26 of the shown in FIG Reactor and for each of the tubes 32 of the shown in Fig. 11-

909811/1020

chosen reactor.

Another useful reactor of the burner type is in Pig. 2 of British Patent 764,082. In using this reactor for the process of the invention, the inert particulate becomes refractory Material in suspension ± in one reaction participant which is introduced in the direction indicated in Figure 2 of this British patent by the arrow 15 is indicated.

The apparatus shown in Fig. 26 for quenching the reaction products comprises a generally cylindrical vessel, which is generally designated 9I and is arranged with its axis perpendicular. A tube 9 ² (made of a suitable metal, for example Inconel), into which the reaction products are introduced, extends horizontally below the vessel, then bends upwards and finally opens into the interior of the vessel 9I through an opening which is formed in the side wall of the boiler near its top.

The boiler 9I has a conical bottom 93, from the center of which elp. Tube 94 extends vertically downward from a small Durohmesser, which is connected at its lower end to the interior of the tube 92. The tube 94 is provided with a control valve 95 for controlling the downward flow of the particulate refractory material in the tube

909811/1028

-6ο- 144275?

Mistake. The particulate refractory material can also be removed from the kettle 91 through an outlet opening 96 formed in the wall of the conical bottom 95 and is provided with a valve 97.

The bowl 9 "is at its / upper end with a middle one Outlet 98 for the quenched reaction products provided, and immediately above the entry point of the Tube 92 is an upwardly sloping baffle plate 99 is provided which prevents the particulate refractory material from the outlet opening 98 in suspension is led out in the gas stream, but this does not prevent the finely divided oxide produced from passing through the opening 98 is brought out.

The pipe 92 is provided with a jacket 100 through which a cooling liquid, for example water, can be passed, and the jacket 100 extends from a position near the lower end of the pipe 9? * To a position near the upper end of the vertical part of the tube 92. Within the vessel ¹ 9 is provided below the point of entry of the tube 92 a plurality of which extends in a direction perpendicular tubes 101 through which can pass a suitable coolant., for example water.

As an example of appropriate dimensions for the deterrent / assumed to be to be used with a burner type reactor that

981 1/1021 'BAD ORlOHNA!

has an inner diameter of about 5 cm, the inner diameter can of the tube 92 be about 5 cm, the lower horizontal part of the pipe 92 be about 1.5 m long and the vertical part of the pipe 92 be about 3 m long. Of the Kettle 9I can have a total height of approximately 1.5 m and an internal diameter of about 30 cm, and the diameter of the outlet 98 can be about 5 cm. The inside diameter of tube 94 can be about 2.5 cm.

The quenching apparatus operates in the following manner: ä A quantity of an inert particulate refractory material, which is preferably the same as that is used for the deposition of the oxide generated to prevent on surfaces of the reactor or to reduce, at first, in the boiler 9I is introduced, and cooling water is passed through the jacket 100 and the pipes 101. The gas stream exiting the reactor, which contains both the oxide produced and inert particulate refractory material in suspension, is fed to the lower end of the tube 92, and the control ^

valve 95 is adjusted to allow particulate matter from the bottom of vessel 91 to flow downwardly through tube 94 into tube 92 at an appropriate rate to permit sufficient quenching of the reaction products. The particulate material from the vessel 9I is entrained in the gas stream within the tube 92 and in this way to the

«09811/1028

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returned upper part of the boiler 9I. The reduction. the gas velocity that occurs when the gas enters the Kettle 9I enters causes the part-shaped refractory Material goes out of suspension and falls into the lower part of the boiler where it is cooled by pipes 101 will. In this way, the boiler 9I works as a settling chute for the particulate refractory material. The cooling jacket 100 prevents the pipe 92 from being attacked by the generated chlorine and prevents precipitation of the generated oxide on the inner surface of the pipe.

From time to time particulate refractory material becomes let out of the boiler 9I through the opening 96 by means of the valve 97, and this material is again introduced into the reactor.

The reactants are preheated advantageous to such an extent that, if they were mixed with each other without any reaction takes place, the temperature of the reactant mixture within the range of 850 ⁰ to 1100 ⁰ C (preferably within the range of 950 ° to 1050 ⁰ C) if the chloride is titanium tetrachloride. The optimal amount of preheat depends in part on the amounts and temperatures of other gases, such as the carrier gas for the inert particulate refractory material and the protective gas introduced into the reaction chamber, with the introduction of amounts of a cooling gas providing greater preheating of the

809811/1028

Makes reaction participants desirable. It is common expedient to preheat the oxidizing gas to a greater extent than the chloride; but if the oxidizing Gas is essentially pure oxygen, it may be preferable to preheat the titanium tetrachloride to a higher degree than the oxidizing gas. The oxidizing gas can be preheated directly by giving it a hot gaseous Combustion product is incorporated which is obtained by burning a fuel gas such as carbon monoxide was, however, each of the reactants, in particular the chloride, is advantageously preheated indirectly, i.e., by passing the reactant through a heated tube or other heat exchange device will. Optionally, the oxidizing gas can be preheated both directly and indirectly. Instead, the Reactants can also be preheated using pebble heaters.

The oxidizing gas advantageously contains molecular oxygen and it can consist of essentially pure oxygen or consist of oxygen mixed with one or more inert gases, for example air or with Oxygen enriched air or ozone.

The choice of oxidising gas depends on the substance of the chloride and, when the reaction is carried out in a reactor of the type of burner, the inner dimensions of the R _e action chamber in a direction transverse to the longitudinal axis of the

BAD ORfQINAL

909811/1028

From the reaction chamber. Other important factors are the extent which the reactants are preheated, and the. Temperature to which the inner surface of the metal part of the Reaction chamber is cooled. The proportion of oxygen in the oxidizing gas is one of the factors that determine the maximum Determined by the gaseous mixture in the reaction zone and the temperature distribution along the temperature Length of the reaction zone is reached. An increase in the proportion of oxygen leads to an increase in the maximum Temperature and a less rapid temperature drop along the length of the reaction zone.

When the chloride is titanium tetrachloride and when the internal dimensions of the reaction chamber are in a transverse direction are small to its longitudinal axis, for example if the reaction chamber is cylindrical and has an inner diameter of about 10 cm or less, there is a risk that the reaction is quenched prematurely if the oxidizing gas is air, and it is then necessary to use an oxidizing gas Use gas that has a higher proportion of oxygen contains, for example, oxygen-enriched air or essentially pure oxygen. The danger of one prematurely holding back the reaction is greater, though however, the temperature to which the inner surface of the metal part of the reaction chamber is cooled is lower this factor is usually less important than the internal dimensions the reaction chamber because, as explained here

9 Ö. 1 1/1 G 2 8 BATH

is the permissible temperature range for the cooled inner surface of the metal part is relatively small. This can reduce the risk of premature deterrence It is suggested that the amount of preheating of the reactants is increased, but very high preheating results to technical difficulties.

The rate of introduction of oxidizing gas into the reaction chamber can be within the range of + 10 % of that required for the gas to react stoichiometrically with the chloride, and is advantageously within the range of + 5% of that rate preferably substantially equal to the rate required for the gas to react stoichiometrically with the chloride. To this end, account must be taken of both the preheated oxidizing gas and any oxidizing gas introduced into the reaction chamber as a carrier gas for the inert particulate refractory.

Advantageously, one is in the oxidation zone Amount of water vapor within the range of 0.05 to 10 Vol. # (Preferably 0.1 to 3 Vol. #) Based on the total volume the gas introduced into the oxidation zone, introduced (the term "gas" is to be understood here to include a vapor).

The water vapor is preferentially in the oxidation zone introduced in mixture with the oxidizing gas. if

909811/1029

H42758

the oxidizing gas is the oxygen present in the atmospheric If there is air in it, it may be found that the air contains enough moisture that none Moisture needs to be supplied. If the air is cleaned to remove gaseous impurities, this can be done in such a way that the amount Water vapor contained in the air remains unchanged or that the amount of water vapor contained in the air is increased. If the inert / particulate Refractory material is introduced in suspension in a carrier gas, moisture can be in suspension in the carrier gas, but this is common not desirable unless the design is such that the carrier gas does not come into contact with the chloride before the chloride mixes with the oxidizing gas.

Various conditioning agents and other agents can be introduced into the oxidation zone. So can for example, if the chloride is titanium tetrachloride and the oxide produced is titanium dioxide, aluminum oxide within of the reactor and incorporated into the titanium dioxide produced to support the formation of rutile, furthermore to improve further pigmenting properties (for example preventing yellowing in oven pine trees) and to make the pigment neutral in the reaction after chlorides are appropriately removed (e.g. by degassing at a temperature of 600 ° C), wherein

909811/1028

the amount of aluminum oxide is within the range from 0.5 to 10 %, advantageously from 0.5 to 4 % and preferably from 1 % to 2.5 % based on the weight of the titanium dioxide product. When a burner type reactor is used, the aluminum oxide can be formed by adding aluminum chloride vapor to the titanium tetrachloride vapor.

The alumina can alternatively be formed by incorporating powdered aluminum metal into the inert particulate refractory material or by introducing powdered aluminum metal in suspension into the titanium tetrachloride vapor. If a fluidized bed reactor is used, the alumina can be formed by introducing aluminum chloride either into the bed (preferably in suspension in the titanium tetrachloride) or into the reactor above the fluidized bed, as described in British Patent 28'414 / 59, which describes a process for the production of titanium dioxide, which is incorporated into alumina, in which titanium tetrachloride vapor and an excess of oxygen or an oxygen-containing gas are formed into a mixture of particles of a refractory material ((which is essentially free of aluminum oxide) existing bed are introduced which is kept in a fluidized state at a temperature within the range of 750 ° to 1500 ⁰ C to the titanium tetrachloride to titanium dioxide to

ORIGINAL BATH 909811/1028

-es- HU758

oxidize, part of which is retained in the bed and the remainder in the gas stream exiting the bed is entrained, and aluminum oxide is incorporated into the entrained titanium dioxide by the aluminum chloride vapor is introduced into the gas stream after it Has left bed and before it cools down to a temperature below 600 ° C, taking the amount of oxygen or of the oxygen-containing gas in the gas stream is at least sufficient to convert the aluminum chloride to aluminum oxide and the rate of introduction of aluminum chloride within the range of 0.5 to 5.0 wt. $ is calculated as aluminum oxide and based on the speed of production of the entrained titanium dioxide.

Further, when the chloride is titanium tetrachloride and the product is titanium dioxide, silicon tetrachloride can be introduced into the oxidation zone to control the particle size of the titanium dioxide product, the amount of silicon tetrachloride (calculated as SiOg) being within the range of 0.05 to 1 jO, preferably from 0.1 to 0.5 wt. $ 6, based on the weight of the titanium dioxide product, is titanium oxychloride, finely divided oxides (e.g. aluminum oxide and silicon oxide), organic compounds ( e.g. hydrocarbons) and titanium esters, which act as nuclei or material for nucleation can also be fed into the oxidation zone.

In addition to the imple mentation of the method in

909811/1028 bathroom ORiQINAL

which the oxide produced is pigmentary titanium dioxide and the chloride titanium tetrachloride are other important ones Embodiments of the method that in which the oxide produced is peroxide and the chloride perrichloride, and that in which the oxide produced is silicon dioxide and the chloride is silicon tetrachloride. If the oxide produced is peroxide, it will be advantageous a fluidized bed reactor is used and the conditions within the fluidized bed are such that at least the greater part of the product is in the form of a deposit on those forming the fluidized bed Has particles which are preferably ferric oxide particles.

The. The invention is explained in more detail below using several examples.

example 1

Titanium dioxide was obtained by the vapor phase oxidation of titanium tetrachloride in a fluidized bed of inert particles using the in Pig. 1 reproduced reactor generated. The reactor had the dimensions indicated above as being appropriate.

The fluidized bed material consisted of hard spherical titanium dioxide particles, the sizes of which were within the range of -22 to +44 BSS sieve meshes, and the mean particle size was 500 4 * (which corresponds to approximately 30 meshes). These particles were made of a fluidic

909811/1028

stripped of a bed of such particles in which titanium tetrachloride had been oxidized to form titanium dioxide. The static depth of the bed was JO cm.

The bed was fluidized characterized in that air (measured at standard temperature and pressure) at a temperature of 95O ⁰ C through the porous plate 2 at a rate of 21.3 nr / h · guided upward. A gas Tocher was introduced into the fluidized bed from the top of the reactor, and as soon as the temperature of the bed had reached a value of 900 ⁰ C, the gas Tocher was removed and increases the feed rate of the preheated air to 42.6 nr / h. At the same time titanium tetrachloride vapor was preheated derauf a temperature of 950 ⁰ C, h supplied through the intake pipes 4 through at a rate of 68 kg /. The titanium tetrachloride vapor contained an amount of aluminum chloride vapor, calculated as AloO ^, corresponding to 1.5 wt. ^, Based on the weight of the titanium tetrachloride, calculated as TiOg

Hard spherical titanium dioxide particles withdrawn from a fluidized bed of such particles in the Titanium tetrachloride had been oxidized to form titanium dioxide, the particle sizes being within the range from -22 to +44 B.S.S., screen meshes were placed in the reactor in suspension at a rate of 45.4 kg / h introduced into the titanium tetrachloride, and they served to block the titanium tetrachloride inlets by AbIa-

90 9811/1028

to prevent generation of titanium dioxide. The speed of these particles in the inlet pipes 4 was 28.7 m / sec. Through the action of the overflow pipe 5 a constant bed depth of 203 cm maintained.

Particulate titanium dioxide product exited the reactor in suspension in the gas stream at one rate of 17 * 2 kg / h and was then fed into a cooling tower, where it was quenched to a temperature below 600 ° C by means of a stream of cold sand. The titanium dioxide was then separated from the sand and gas stream by means of a conventional system of cyclones and bag filters.

The titanium dioxide was then hindurehgeführt by a rotary kiln in which it was its temperature was raised to 650 ⁰ C and held for 2 hours at this value in order to decompose absorbed gases, such as HGL and CIP * to remove any titanium oxychlorides, which can be present.

The product obtained had an average particle size of from 0.3% ^ M and a tinting strength of I650 (after the Reynold-scale), and it was completely in the rutile form.

Example 2

Titanium dioxide was produced by a vapor phase reaction between a preheated oxidizing gas and a preheated gas

BAD ORJQlNAL

909811/1028

- η - 1442756

Titanium tetrachloride vapor using the in PIg. 9 reproduced Reactor generated. The reactor was made entirely of silica and had the above as useful specified dimensions.

The "titanium tetrachloride vapor wurde.auf eine.Temperatur of 950 ⁰ C and pre-heated in the reaction chamber I7 through the inlet pipe 21 passing at a rate of" introduced in 2000 kg / h. Protective gas in the form of chlorine was supplied at room temperature through the area between the tubes 21 and 22 at a rate of 28.3 nm / h (measured at standard temperature and pressure).

Moist air (saturated at a temperature of about 21 ⁰ C) was preheated to a temperature of 950 ° C and reaction chamber YJ introduced the in through the pipe 19 back ■ by a rate of 12JQ r / b .. Therefore, The amount of Viasserdampf introduced into the oxidation zone was 2.3 vol. $>, based on the total volume of the gas introduced into the oxidation zone. Cold silica sand having a particle size within the range of -10 to +22 BSS sieve meshes was fed through the pipe 20 at a rate of 227 kg / h, the flow being controlled by a vibratory feeder. . .

A molten mixture consisting of 40 wt \% Natriumnitritj, 7 wt.% Of sodium nitrate and 53 weight% potassium nitrate was. And a Sahmelzpunkt of 142.2 g was

9 0 9 8 1 1/1 0 2 8 -. ,, ^ AD Oriqinal

passed through the cooling jacket 18, and on this Way, the outer surface of the reaction chamber I7 was on a Temperature kept within the range of 260 ° -270 ° C, which is an estimated indoor doorway of about 600 ° C (the V / and the reaction chamber I7 had a thickness of 19 mm).

When leaving the reactor, the titanium dioxide product was quenched, collected and degassed, as described in Bf) I-spif 11. The final product had an average particle size of 0/25 , {{ and a dyeing power of 1550 (after dor Reynold-Ckal.ii.).

Example j?

Titanium dioxide was Żwir by a Dampfpharenreaktion; -:... Aen a preheated oxidizing gas and vorarhitztern Titantotrachloriddampf using again ^ ogebenen and in accordance with the generated b'ig in Fig '(8 modified reactor Dor reactor was made entirely of silica and h'ftte the dimensions given above as being appropriate.

The tetrahydrofuran vapor, which had been preheated to a temperature of 950 ° C., was fed into the reaction chimney or * 9 through the pipe 15, the distributor space 12 and the hole 16 at a rate of 629 kg / h introduced. The titanium tetrachloride vapor contained an amount of aluminum chloride vapor, calculated as AIoO. ,, corresponding to 1 Qr.-vi. '/ J, based on the weight of the titanium tetrachloride,

BATH

909811/1028

calculates as TiO ₀ . Λ- .-

Atmospheric air was removed by a liquid purge. Longer in Hindu to remove gaseous and solid impurities, and then ^{preheated to a temperature of 950 0} C and into the reaction chamber 9 through the opposite inlet pipes 14 through at a rate of 2265 rrr / h (measured at standard temperature and pressure) introduced ". the air" containing about 0.01 kg of steam per "kg dry air _o Therefore, the amount of introduced into the. oxidation zone water vapor 1.3 vol · / ^, based on the das.Gesamtvolumen in the Oxidation zone of introduced gas.. ■ -. ■. ■ ■.

Cold silica sand, the particle sizes within the range of -10 to + 36 BSS mesh openings had 2 kg / cm was in the reactor through the drilling means of compressed air through I5> at einem'Druck of K, introduced. The speed of the sand feed was 227 kg / h and the speed of the compressed air feed was 113 ir / h (measured at standard temperature and pressure). Was a molten mixture consisting of 40 wt. ^ Natriumriitrit, 7 wt.% Of sodium nitrate and 53 wt. ^ I potassium nitrate and a melting point of-142.2 had ⁰ C, was passed through den'Mantel 10, and enough this to to keep the outer surface of the Reaktiönä'kammer at a temperature of 270 ⁰ C, a geEschätzten Innenflächehtempera'tur of "βυ ^{©: ': i: -:'} Ö ^f corresponded. ^';.

The Titaridioxydproduktv ^; -das ^{1 !:} mlt ^r ^ \ tner "^; Ges ^! chw ^ drgke; i ^^

909811/10 2i ^vf

BATH

of 1470 kg / h was produced, was treated as described in Example 1, and the end product had a Pärbekraf.t of 16OO (according to the Reynold scale) and a mean particle size of 0.27 / (, and it was completely in the rutile form.

. ■■■ ··,: .., - .. Example 4

Titanium dioxide produced by a vapor phase reaction between an oxidizing gas and vorerh i tzten Titantetraehloriddarapf preheated using the procedures described in the figures 11 and 1.2 reactor that had the above dimensions specified as the appropriate *

Titanium tetrachloride vapor and moist oxygen was preheated to a temperature of 850 ⁰ C and then the reaction chamber 29 through the inlet pipes 30 and $ ~ Λ hindutih at a rate of 1000 kg / h or / h supplied 59ΟΟ kg.

Silica sand particles, the sizes within the range van -10 to +20 B.S.S. sieve meshes were in the reaction chamber 29 through the tubes J2 by means of Compressed air at a pressure of 4.2 kg / cm was introduced. The sand feed speed was 3½ kg / h, and the speed the compressed air supply was 1 Tj5, 1117h. (measured at standard temperature and pressure). .

The word dor temperature within the reaction chamber 29 at a short distance downstream of the reactant partner inlet pipes 30 and 3I was increased to 13po ° C _; appreciated, and the

BATH

90981 1 / 102ii Cf ^ - ■

^; ' ^: -76- ■ , 1U2758

dwell time within the reaction chamber 29 was approx 0.1 second. , _ ■ ...-.

The titanium dioxide product. which was generated at a rate close to the theoretical maximum yield of 2450 kg / h or 58.8 t per day, was quenched when leaving the reactor to a temperature below 600 ° C o After the titanium dioxide from the sand was separated using settling chambers, it was checked and it was found that the mean particle size was within the range of 0 _Λ 2 to 0.3: ... The staining power was 1400 (on the Reynold scale ), ..and . the rutile content was 7 % - the process was continued over a period of more than 200 hours'. without blocking the reactant inlets. *

5.

. Titanium dioxide was oxidized by a vapor phase reaction between a previously heated; Gas and preheated mi. Tiftantetrachloriddampf using the in Fig .7 "said given reactor How-generated, ^ was, however, the pipe I3, replaced with the reproduced pipe in Fig 25 ^ 87" De _r.:. .Reaktor was made entirely of silica -In. The reactor shown in Fig. 7 had the reaction chamber 9 ^: an inner diameter of 50 mm and an length of approximately 2.4 m, the inner diameter of the esophagus. " IJ and 14 are I9 mm :, and the axes of the food

BATH

Tubes 14 were arranged at a distance of '{6 mm from the upstream end wall of the reaction chamber. The manifold um 12 was 102 mm long and had an inside diameter of 89 mm. There were six slots 11, each 57 mm long and 2.1 mm wide. The inside diameter of the main part 89 of the tube 87 was 12.7 mm and the inside diameter of the end part 88 was 6.35 mm.

The reaction products were prepared using the in Fig. 26 quenched device which the above al :; appropriately specified dimensions had.

Liquid titanium tetrachloride was made in a stainless steel. The boiler was evaporated, and the resulting steam was heated to a temperature of 120 ° C. by being passed through a Yor heater, which was made up of a silica system, which was heated outside with Filffj von Ctadtg ^ s. The vorerhit ^ te titanium tetra chloride vapor, the 12 jo aluminum chloride (calculated · alfj -AIpO _7), based on the weight of the Titantetraehlörids (calculated as TiO ₀₎ was wurrl "duruh the Speis'erohr '\'j> the Vortoilcrraum 12 kg at a rate of Ij6 / h fed to the speed of the Titantetrachlbrid- (\ -. mpfes in its passage through the slots 11 before it enters the Rcaktionskammer 9 was su "ung'.fähr 28.7 m / sec immediately appreciated.

Couorr.toff was tempered to a temperature of 1000 G in

BATH

90981 1/1 028 '

a preheater, which is a'us a silica pipe system that was heated outside with the help of town gas. The preheated oxygen became the reaction chamber 9 through the opposite feed pipes ^ .through at a speed of .13 * 3 nr / h (measured at normal temperature and normal pressure). The oxygen contained 2.75 vol / d water vapor, based on the total volume of the gas introduced into the reaction chamber 9 »

Silica sand, which consisted of particles, the sizes within the range from -10 to + 4Q-B.S.S.-sieve mesh had, ii-> the reaction chamber 9 through the pipe 8-7 introduced therethrough by means of compressed oxygen. Of the

P pressure of this oxygen was K, 2 kg / cm, and it was (as measured at normal TemperELtur and pressure) through the tube 87 with a · speed of 4.53 m / h züge- leads. The rate of supply of sand, which was regulated by a vibrating feeder, was 45 kg / h, so that the concentration of sand in the carrier oxygen was 10 kg per cubic meter of carrier oxygen. The temperature of the mixture of sand and carrier oxygen immediately before - their .... introduction Ln the. The reaction in chamber 9 was JQQ ⁰ C and it was estimated that the rate of the mixture at this point was approximately 86.2 m / sec.

A molten mixture consisting of ¹ of 40 wt. Sodium nitrite, 7 wt. fo sodium nitrate. and 53 wt ^ of potassium nitrate and also having a melting point of ^'1 i42,2 ° C had been con-

- ■■ "■ - ' ^: '■.-'-; ■ - 6ADORiQINAl.

9098 1 1/1 02 8 ..- V ^{ΓΛ v} - ^!: "V ^ K

continuously through the jacket 10 and a Vi arms from ta. rather circulating dropped as, in which cooled das'Salzgemisch. · In this-was catfish the temperature of the inner surface was kept the wall of the Röaktionskammer 9über the length of the sheath 10 on an estimated temperature of 650 ⁰ C *

The gases leaving the reaction chamber 9, which both Silica sand and titanium dioxide produced in suspension were poured into the lower end of the (made of Inconel)

standing) pipe 92 of the in Fig. 26 as the given stretching device was introduced, the pipe 92 being cooled with the aid of water which was passed through the cooling jacket 100. The temperature of the reaction products as they enter the tube 92 was 1000 ⁰ G, and their overall 'speed in this "point-was estimated to be about 21.3 m / see.

The vessel 9I contained Kieselerdeεand, which was the same as that - 'was inserted into the Re s.kti ons chamber 9 through the pipe 87 therethrough, and the control valve · * 95 was adjusted so that this sand through the pipe ^ k ... "at a rate of I250 kg / h by passing went down. the tubes' 101 away heat from the sand in the vessel 91, and the sand came out of the vessel ¹ with a temperature of 35 ° C in the tube 94 From time to time, sand was withdrawn from the discharge point 96 by opening the valve 97 to compensate for the sand which was carried out of the reactor:; carried into the pipe 92

BATH

9098 t 1/1 028 ■ - ■ - ':.': -

-so -

Sand was reintroduced into the reaction chamber 9 via pipe 87. ^ \ :

After leaving out of the vessel via the outlet 9I ¹ 'was 98, the gas stream containing the titanium dioxide produced in suspension ,, by a conventional Äbtrennsystem which cyclones and bag filters had to separate the Titandioxydprodukt of the gases.

The Tltaridioxydprodukt was treated as described in Example 1, and the final product had a tinting strength of 1600 (after the Reynold scale.) And an average particle size of 0.32 M ä> ^{un it} l- ^a -S completely in the rutile form

. · - ■ _; . .. ■. , -.- _BAD 909811 / IQ ZB '

Claims (7)

Claims α Λ Λ 9 7 RR for the production of an oxide of one of the elements titanium * -. zirconium, iron, aluminum and silicon by reacting a: chloride of the element with an oxidizing gas in the vapor phase, in which the chloride and the oxidizing gas are preheated to such an extent that, if they were mixed together without reacting, the temperature of the resulting mixture misehes would be at least 700 C, and the preheated chloride vapor and the preheated oxidizing gas are introduced into a refueling chamber through separate inlet devices in such a manner that a swirling stream is pre-introduced; intimately mixed gases is generated in which the oxide is formed in finely divided form, characterized in that an inert teilohenförniiges refractory material is introduced into Cie reaction chamber in such a manner that, et; impinges on the reactor surface or surfaces which are immediately adjacent to the Gfiseinlaßvorrichturigen and accessible to the two reactants, in order to prevent the deposition of generated oxide on the surface or surfaces or to considerably reduce that the particulate refractory material at least substantially out of the Reaktjonskammer is led out in suspension in the swirling gas stream and that thereafter the particulate material is separated from the oxide produced by the dome. Gf? L (3lNAL 9 0 9811/1 028 ν _<; ., ^ ₀ 2.) Method according to claim 1, characterized in that that the oxide produced is pigment-like titanium dioxide and that Chloride is titanium tetrahalloride .. 3 ») Method according to claim 1 or 2, characterized in that the reaction in a reactor of the -mit fluidized bed working ^ type is carried out. 4.) Method according to claim 1 or 2, characterized in that that the reaction takes place in a reactor of the burner type is performed. 5 «) Process according to claim \ -, characterized in that the reactants are introduced into the reactor through -paralleIe inlets and that the flow rate of the gaseous mixture within the oxidation zone corresponds to a ReynoId flow number of at least 50,000« 6.) Method according to one of claims 1 to 5 * thereby characterized in that the inert, part-shaped refractory Material made from zirconia particles, borrowed from alumina or from ■ Titanium dioxide is composed of a fluidized Bed of titanium dioxide particles have been stripped off in a process for the production of titanium dioxide by the Vapor phase oxidation of titanium tetrachloride within the Bed is used. 7 ») Method according to one of claims 1 to 5, characterized characterized in that the inert, particle formigo-refractory Material consists of Kieselerdeεand. 90981 1/1028. ^ n- -. " BATH .83-144275 8.) The method according to any one of claims 1 to "], characterized in that substantially all of the particles of the inert, particulate refractory material have sizes of +85 BSS, screen mesh. 9.) Process according to claim 8, characterized _s that substantially all the particles of the inert particulate ,, .feuerfesten material have sizes within the range of -8 to +30 BGS SiebmaGchen .. -.;. IQ.-) Method according to one of claims 1 to 9 "da—" characterized in that the inert, particulate refractory material is introduced into the reaction chamber at a rate of at least JO m / sec. 11.) - Process according to one of Claims 1 to 10, characterized in that the inert, partially shaped refractory material is introduced into the reaction chamber at a temperature which is substantially lower than the temperatures at which the preheated oxidizing gas and the preheated Chloride can be introduced into the reaction chamber. λ 12,) Method according to one of claims 1 to 11 _Ä, characterized in that the / inert, particulate refractory material is introduced into the reaction chamber in suspension in one or in both of the preheated reaction partners. 13.) The method according to claim 12, characterized in that that the inert, particulate refractory material in the Roaktionsko.mmer in suspension in the preheated BAOORtQiNAL 909811/1028 '"■"' ■■ -'-. / - 84 - H42758 oxidizing gas is introduced. - ^: 14.) Method according to one of claims 1 to 1'1, characterized in that at least part of the inert., particulate refractory material into the reaction chamber in suspension in one or more streams of a carrier gas is introduced by inlet streams separate from the inlet streams for the preheated reactants are. . . - "' 15.) The method according to claim 14 / characterized in, that the carrier gas is directed so that it is the inert particulate causes refractory material to impinge directly on the reactor surface or surfaces, the gas jetting devices are immediately adjacent and accessible to both reactants. 16.) Method according to claim 14 or 15 *, characterized in that that the inert rga, s is an inert gas. 17 ·) Method according to claim 16, characterized in that the carrier gas consists of chlorine or nitrogen. 18.) The method according to claim 14 or 15 * thereby ge = indicates that the carrier gas is an oxidizing gas that has not been preheated in the specified manner. 19.) The method according to any one of claims 14 to 18, characterized in that the carrier gas is introduced into the reaction chamber at a temperature which is not greater than 15Q ⁰ C ,. . - _ 20.) Method according to claims 3 and 14 * thereby 909811/1028 ORIGINAL BATHROOM characterized in that the chloride is in the fluidized bed through one or more gas inlet lines is introduced leading to inlet openings which are flush with the inner surface of the side wall of the reactor, and that a stream of the carrier gas containing the suspended particulate refractory material into the or Each such gas inlet conduit is introduced at a short distance from the inlet port, the flow being so designed and / or directed to be placed on the wall of the J Line hits over the entire end part of the line. 21.) Method according to claim 2Q, characterized in that that the or each stream of carrier gas is introduced through a nozzle which is coaxial, in a chloride inlet duct is arranged at such a distance from the open end of the conduit that the exiting from the nozzle conical jet of suspended particulate refractory material directly onto the wall of the end portion of the Line hits. 22.) The method according to claim 21, characterized in that " that the or each stream of carrier gas enters a chloride inlet line introduced in a tangential direction and either perpendicular to the axis of the conduit or so directed becomes that the current is a component of motion in the Has the direction of flow of the chloride along the line. 23.) Method according to claims 4 and 14, characterized characterized in that the reaction chamber is generally cylindrical BAD ÖRtQiNÄt 909811/1028 -86-, 1442753 is that the one reactant in the reaction chamber through one or more inlet openings in the side wall the reaction chamber is inserted through, the other Reactants in the reaction chamber at an upstream of said inlet opening or openings and the carrier gas is introduced into the reaction chamber through a nozzle which is coaxial is located in the reaction chamber and upstream of the inlet opening or openings in the side wall of the chamber, so that the conical jet emerging from the nozzle of the suspended particulate refractory material impinges directly on the reactor surfaces, the inlet or the Adjacent inlets in the side wall of the reactor. 24.) The method according to claim 23, characterized in that that the chloride enters the reaction chamber through the inlet port or openings in the side wall of the reactor. and that the oxidizing gas is introduced into the reaction chamber at a point upstream of said inlet opening or openings is introduced. 25.) Method according to claims 4 and 14, characterized characterized in that the chloride and the oxidizing gas in the reaction chamber can be introduced through inlets which are arranged coaxially to one another, so that the carrier gas is introduced through an inlet which half of the inner inlet line is and so arranged is that it creates a conical beam of the suspended part 909811/1028 .87-144275 Chen-shaped refractory material directed towards the inner surface of the end portion of the inner inlet duct. 26.) The method according to claim 25, characterized in that that the chloride enters the reaction chamber through the innermost Inlet is introduced therethrough. That the oxidizing Gas is introduced through the surrounding inlet and that further particulate refractory material is introduced into the reaction chamber in suspension in the oxidizing gas and thus caused to hit the outer surface f of the end part of the chloride inlet line. 27.) Method according to claims 4 and 14, characterized characterized in that the carrier gas is introduced through an annular inlet having an inlet for the Chloride or the oxidizing gas surrounds and is arranged so that it creates a converging stream of suspended Particles aimed at the reactor surfaces, which this inlet for the chloride or for the oxidizing gas directly surround. j 28.) Method according to claims 4 and 14, characterized characterized in that the carrier gas containing particulate refractory material in suspension is passed through an inlet is introduced therethrough, which is within a reactant inlet line lies and is arranged so that it has a conical beam of the suspended particulate refractory material directed towards the inner surface of the end portion of the reactant inlet conduit, and that further BAD ORfQINAt 909811/1028 Carrier gas j which particulate refractory material - in Contains suspension, through an annular inlet - is introduced through, which is fed by this line Surrounds reactant inlet and is arranged to have a converging stream of suspended Particles aimed at the reactor surfaces, which-these Surrounding the inlet immediately. "". ' 29.) Method according to claims 4 and 14, characterized characterized in that the chloride and the oxidizing gas in the real chamber can be introduced through inlets, whose axes run parallel to each other and are arranged side by side, and that the carrier gas through a or more 'inlets is introduced through', which are connected to their axes parallel to the axes of the reactant inlets and upstream of the reactant inlets lie. 30.) The method according to claim 29, characterized in that that part of the particulate refractory material into the reaction chamber in suspension in the oxidizing Gas is introduced. "; - ■ - ■■ _ .. ■ 31.) The method according to claim j50, characterized in that that the carrier gas, which contains particulate refractory material in suspension, into the reaction chamber introduced through a movable nozzle device will. - J52.) Method according to claim 30, characterized in that 90 Ö 8 1 1 / f 028 BAD ORfillNÄL net that further carrier gas through into the reaction chamber a fixed inlet device is inserted through » 33) Method according to claim 32, characterized in that that the carrier gas that is in the reaction chamber through the. solid inlet device is introduced through, is continuously supplied, and that the carrier gas passing through the movable nozzle device is inserted therethrough, is intermittently fed. 34.) The method according to any one of claims 1 to 33 * d characterized in that the reactor surfaces which are accessible to the mixed reactants and / or to the hot oxide produced are cooled indirectly with the aid of a coolant. 35 ·) Method according to one of claims 1 to 3 ^ ·, characterized characterized in that the reactor surfaces, the inlet device for the chloride and / or the inlet device for the oxidizing gas are adjacent, are cooled indirectly with the aid of a coolant. 36.) Method according to claim 3 ^ or 35. » characterized denotes overall%, at least a portion of the reactor consists of metal and that all metal surfaces, which are accessible for the chloride or for the produced in the reaction of chlorine, are cooled to a temperature which is above the dew point of the chloride and the Corrosion temperature of the metal does not exceed 37.) Method according to claim 36, characterized in that BAD ORIQlNAU 909811/1028 that the metal is nickel, that the chloride is titanium tetrachloride, and that all nodding areas, which · for the titanium · tetrachloride or for the chlorine produced are accessible, indirectly to a temperature within the range of 140 ° to 325 ° C. 38.) The method according to claim 34, characterized in that the reaction ^{temperature is within the range of 1000 ° to 1300 0} C, that at least a part of the reactor consists of a non-metallic heat-resistant material and that all surfaces of this material that are for the Chloride or for the .generated chlorine are accessible, are cooled ^{to a temperature below 9OC) 0 C.} . · 39) The method of claim 38, - characterized in that the on-off · dem.nicht-metallic refractory material existing surfaces which are accessible to the chloride or for the generated chlorine, ⁰ C are cooled to a temperature below SOO. 40.) The method of claim 39 1 characterized in that the non-metal from the refractory material existing surfaces which are accessible to the chloride or the chlorine produced can be cooled to a temperature which does not exceed the 65O ⁰ C. 41.) Method according to claim 36 or 37 * thereby ge » indicates that the coolant used consists of water, Water vapor or oil. 42.) Method according to one of claims 38 to 40, ί ·; ■■ 90 9 811/1 0 2 8 BAD _ 91 - 1442756 characterized in that the coolant used consists of a molten metal salt or a molten mixture of metal salts. 4j5.) Method according to claim 42, characterized in that that the coolant is a molten mixture consisting essentially of 40 wt. $ sodium nitrite, 7 .wt. # Sodium nitrate and 53 wt. # of potassium nitrate and a melting point of about 141.2 ° C. 44.) A method according to any one of claims 38 to 40, M DA characterized by that the non-metallic refractory material is comprised of silica. 45 ·) Method according to one of claims 34 to 44, characterized characterized in that the reaction chamber is generally cylindrical and has a diameter not smaller than that than 10 cm. 46.) Method according to claim 45, characterized in that that the minimum diameter of the reaction chamber is not is smaller than 15 cm. · 47.) Method according to one of claims 1 to 46, characterized in that at least one reactant inlet device either from another reactant inlet or the reaction chamber wall from an inert gas inlet is surrounded and / or separated, through which a protective gas that is inert to the two reactants is inserted into the reaction chamber. 48.) The method according to claim 47, characterized in that BAD ORfQlNAL 9098.11 / f 028 that the protective gas consists of chlorine. - 49.) Method according to claim 4-7, characterized in that the protective gas consists of nitrogen. . 50.) The method according to any one of claims 47 'to 4-9 , - there, -, characterized in that the protective gas is introduced into the reaction chamber at a temperature of at least 150 ⁰ C and that the speed of the protective gas immediately "before its introduction into the reaction chamber is at least 30 m / sec. 51.) The method according to claim 50, characterized in that the speed of the protective gas immediately before its introduction into the reaction chamber is about 90 m / sec » 52.) The method of claim 50 or 5I> characterized in that the protective gas is introduced into the reaction chamber at a temperature within the range of 600 ° to ⁰ 1QOO C. 53 ·) "Method according to one of claims 47 to 52 > characterized in that the chloride is introduced through an inner tube into a stream of oxidizing gas flowing inside the reaction chamber and that an inert protective gas is introduced into the reaction chamber through an outer tube Tube e is introduced, which is coaxial with the inner tube and ends flush with the end of the inner tube. ■ 54.) Method according to claim 4 and one of the claims 47 to 52, characterized in that the chloride and the 009 8 11/1028 -95- H42758 oxidizing gas can be introduced into the reaction chamber through inner and outer coaxial inlets and that the protective gas into the reaction chamber through a third coaxial inlet is introduced therethrough between the inner and outer reactant inlets. · 55) A method according to claim 54, characterized in that additional inert gas is introduced into the reaction chamber through a fourth reactant inlet through which d nereinlässe surrounding the outer of the two coaxial Reaktionspart-. 56.) Method according to claim 4 and one of claims 47 to 52, characterized in that the oxidizing Gas and the chloride into the reaction chamber through inlets are introduced through, which are not arranged one inside the other, and that the protective gas into the reaction chamber through one or more inlets is inserted therethrough, which the inlet or inlets for at least one. surrounding the reactants. 57.) Method according to claim 4 and one of claims ™ 47 to 52, characterized in that the oxidizing gas is caused to flow along the reaction chamber, and chloride in the flow of the oxidizing gas through a Slot in the wall of the reaction chamber inserted therethrough that the chloride will first pass through an outer slot which is narrower than the slot in the wall of the reaction chamber is fed to a ribbon-shaped stream of the ChIo- BAD ORiQINAL 0 9 811/10 2 8 ■ -, ■ 9 * -. 1,42758 to form rids, and that the protective gas in the reaction chamber ' mer through the slot in the wall of the reaction chamber is introduced on both sides of the ribbon-shaped chloride stream. 58.) Modification of the method according to claim 3 1, characterized in that the inert, particulate refractory material remains in the fluidized bed and forms part of it. 59 ·) Method according to claim 58, - characterized in that that the particles of the fluidized bed and the inert ones refractory particles are made of the same material. 60.) The method according to claim 59 *, characterized in that that the inert refractory particles are obtained by operating them from another fluidized bed Process for the oxidation of the chloride deducted will. 61 ..) Method according to claim 59, characterized in that the inert refractory particles are thereby obtained are that particles are withdrawn from the fluidized bed and the size of the withdrawn particles is reduced will. 62.) Method according to one of claims 1 to 57 * thereby characterized in that the oxide produced from the inert particulate refractory material using ^ a settling chamber is separated. ■ 63 ..) method naoh one of claims 1 to 57 or 62, j -j Q-2 § BAD ORIGINAL -95- '14 * 2758 characterized in that the inert particulate Refractory material cooled after separation from the generated oxide and then returned to the reaction chamber will. 64 ») Method according to one of claims 1 to 6.5, characterized characterized in that the residence time of the Roaktionspartners and the product in the oxidation zone is in the range of 0.02 to 1-0 seconds. 65 ») Method according to one of claims 1 to 6 ~ $, characterized in that the oxidizing gas consists of oxygen or oxygen-enriched air and that the residence time of the reactants and the products in the oxidation zone is approximately 0, 01 second. 66.) The method according to claim 6k or 65, characterized in that the gaseous reaction products with the generated oxide in suspension for a period of time in the range from 0.01 to 10 seconds from the point in time of the introduction of the chloride into the oxidation zone of a treatment be subjected to a temperature below 90O ^{0 C for quenching.} 67.) The method of claim 66, characterized in that the reaction products are quenched to a temperature below 65O ⁰ C. 68.) The method according to claim 66 or 67, characterized in that the gaseous reaction products for a period in the range of 0.05 to 5 seconds from the time 11/10 2 8 ^mö ORDINAL must be quenched at the point of introduction of the chloride into the oxidation zone. 69.) Method according to one of claims 66 to 68, characterized in that the quenching is effected in that cooled product gas is mixed with the product gas stream which contains the generated oxide in suspension. . . ■ 70.) The method according to claim 69, characterized in that that the cooled product gas consists of cooled generated chlorine. ■ 71 · :) "Verfahreil according to any one of claims 66 to 68, characterized in that the quenching is effected by a cold inert teilchehförmiges refractory material is däspergiert in the product gas stream, which is then separated from the reaction products, 72.) The method according to claim 71, characterized in that the particle-shaped material that is used to bring about the deterrent is used; is composed of the same substance as the particulate material, which is used to prevent or reduce the deposition of the generated oxide on reactor surfaces. 73 ·) Method according to claim 72, characterized in that that part of the separated particulate material returned to the reactor to be used the deposition of the generated oxide on reactor surfaces, to prevent "or belittle. 909811/102 8 74.) The method according to any one of claims 71 to 73, characterized in that the inert particulate refractory material which is used for the quenching, and the inert particulate refractory material which is introduced into the reaction chamber, from the product gas stream upwards to a device is performed, the dds separated inert particulate refractory material is used to separate the inert particulate refractory material from the gas stream and cooling, the part is then returned under gravity from a, to deter other reaction products to bring about, and a portion of which is returned to the reaction chamber. 75 ·) The method according to claim 2 and one of claims 5 to 74, characterized in that the reactants are preheated to such an extent that if they were mixed with one another without a reaction taking place, the temperature of the reaction partner mixture is within the range of 85O ⁰ to 1050 ⁰ C would be. \ 76.) The method according to claim 75 *, characterized in that the reactants are preheated to such an extent that, if they were mixed with one another without a reaction taking place, the temperature of the reaction partner mixture within the range of 950 ° to 1050 ⁰ C would lie. 77 ·) Method according to claim 75 or 76, characterized in that BAD ORIQlNAL 809811/1028 indicates that the oxidizing gas consists of essentially pure oxygen and that the chloride in one
greater extent than the oxidizing G \ s is preheated. 78.) Method according to one of claims 1 to 77 * thereby characterized in that the oxidizing gas is thereby preheated is that in this directly a hot gaseous combustion product is introduced, which by the Combustion of a fuel gas is obtained. . 79 ·) Method according to claim 78, characterized in that that dis fuel off gas consists of carbon monoxide. 80 *) Method according to one of claims 1 to 77 > characterized / that each of the reactants is preheated indirectly by passing the reactant through an externally heated heat exchange device. . ". '" 81.) Method according to claim 1 or 2, characterized in that the oxidizing gas is molecular oxygen
contains. :. 82.) A method according to claim 81, characterized gekennzeich- ⁼ net that the oxidizing gas of substantially pure
There is oxygen. 85.) Method according to claim 81, characterized in that • - net that the oxidizing gas comes from air or from oxygen enriched air. 84.) Method according to one of claims 1 to 83, characterized in that the speed of introduction 9098 11/1 02 8 BAD ORIGINAL 1442718 of the oxidizing gas into the reaction chamber within the range of + 10 % of that which is necessary for the gas to react stoichiometrically with the chloride. 85ο) The method according to claim 84, characterized in that the rate of introduction of the oxidizing gas into the reaction chamber is within the range of +5 % of that which is necessary for the gas to react stoichiometrically with the chloride. 86.) Method according to claim 85 *, characterized in that the chloride and the oxidizing gas in the reaction chamber in substantially stoichiometric proportions to be introduced. 87.) Method according to one of claims 1 to 86; through this characterized that in the Oxydationsζone a lot Water vapor is introduced which is within the range of 0.05 to 10 vol. $ Based on the total volume of the base introduced into the oxidation zone. 88.) Method according to claim 87, characterized marked- ^ net that a lot of water vapor is introduced into the oxidation zone that is within the range of 0.1 to 3 Vol "$, based on the total volume of the in the oxidation chamber imported gas, lies. 89.) The method according to claim 87 or 88, characterized in that the water vapor in the oxidation zone Mixing with ^ lem oxidizing gas is introduced. BATH 909811/1028 1442718 90.) The method of claim 2 and any of claims 3 to 89 characterized in that formed within the reactor and aluminum oxide in the titanium dioxide produced: is introduced, wherein the Aluminiumöxydmenge within ^v "of the range of 0.5 to 10 wt ^. based on the weight of the titanium dioxide produced; » Process according to claim 90, characterized in that ^: the amount of aluminum oxide is in the range from 0.5 to 4 % , based on the weight of the titanium dioxide produced VV V; ■■; ■■■ - ■■ - '' --- ^: ■ V-VV: VV 92.) Procedure according to Anapruoh 9I, thus marked .net that the Äluminiumoxydrnenge in the range of 1-Miis -'-- '2.5 % » based on the weight of the titanium dioxide produced, is; ■: V V .; v; '.-ν- ■ -; ■■ ": \' - ■ ^: " · ^: ' ^: - ^{; i} - ' 934) 'method according to claim 4 and one of claims 90 to 92i · characterized in that the aluminum oxide is formed in that aluminum chloride vapor is introduced into the titanium tetrachloride vapor. ^: - 9 ^ »5 method iiäeh" claim 4 and one of claims 90 to 92, characterized in that the aluminum oxide. · Daduroh that powdered aluminum metal is introduced into the "reaction chamber. · · \ - . .95 ·) * Disposal according to claim 9%, characterized in that the pulverulent aluminum metal is introduced into the oil reaction chamber mixed with the necessary refractory material; becomes * _,; ; _ä -; - ^> '- BAD ORIGINAL 909811/1018 /> 1442759 9β.) Method according to claim 9 ^, characterized in that that the powdered aluminum metal in the reaction chamber is introduced in suspension in the titanium tetrachloride vapor. 97 ·) Process according to claim j5 and one of claims 90 to 92> characterized in that the aluminum oxide is formed by introducing aluminum chloride vapor into the reactor above the level of the bed before the gas flow leaving the bed drops to a temperature below 600 ° C has cooled. 98.) Method according to claim 2 and one of claims 3 to 97 * gekennaelehnet that silicon tetrachloride is introduced into the oxidation zone, the amount of silicon tetrachloride (calculated as SiO ₂ ) within the range of 0.05 to 1.0 wt. ^, based on the weight of the titanium dioxide produced, is 99 ·) Process according to claim 98, characterized in that the amount of silicon tetra-chloride is within the range from 0.1 to 0.5% by weight, based on the % by weight of the titanium dioxide produced. 100.) Method according to Claim 3 * characterized in that that the oxide produced is ferric oxide and the chloride is ferric chloride and that at least a major part of the product is in the form of a deposit on the parts that make up the fluidized bed. 101.) Method naoh Anspruoh 100, thereby gekennzeloh- ι ORfQJNAL 909811/102 0 1442738 net that the part of the bed forming the fluidized bed Ferrioxyd exist. 102.) Method according to claim 3 *, characterized in that that the oxide produced is silicon dioxide and the chloride is silicon tetrachloride and that at least one larger one Part of the product is in the form of a deposit on the particles which form the uidized bed. 103.) The method according to claim 102, characterized in that that the particles forming the fluidized bed consist of silica. 909811/103 "BADOH ₁₈₁ NAL