DE1048877B - Process for the production of halogen-containing carrier catalysts - Google Patents

Description

GERMAN

PATENT OFFICE i.

kl. 12 g 4/01

INTERNAT. KL. BOIj

COfO

U 4806 IVa / 12 g

SEPTEMBER 27, 1957

Jt E CAN MAKE UNG LOGIN

AND ISSUE OF THE

iUSLEGESCHRlFT: 2 2.JAINiJAK 195 < >

Catalysts containing Eriedel-Crafts metal halide and various methods of producing them are already known. Although these catalysts have wide industrial utility because of their short life and uncontrollable activity so far used very little. The invention is based on Finding that catalysts of particularly high activity and long service life with the help of Aluminum halides !! by the following in a - /. a manufacturing processes described can be produced.

The method according to the invention consists in leaving an aluminum halide. / .. B. chloride or r.romid. onto a previously prepared mass, consisting of a refractory oxide as a carrier and a metal that is active in hydrogenation reactions and selected from groups Via and VIII of the Periodic Table (hereinafter referred to as "Ilydrier constituent"), and then bandaged the so treated The mass is heated to a temperature above 300 ° C. until practically all of the unreacted aluminum halide has been removed therefrom.

In a particular embodiment of the process according to the invention, aluminum chloride is evaporated or aluminum bromide on a previously prepared mass of alumina and a metal of Platinum group and heated the mass treated in this way to a temperature above 300 ° C long enough to to remove practically all of the unreacted aluminum halide therefrom. In particular takes place in a certain embodiment of the invention, the catalyst preparation by using aluminum chloride sublimed onto a preformed mass of platinum and aluminum oxide and treated in this way The mass is heated to a temperature of about 400 to 600 ° C for at least 1 hour and until virtually all of the unreacted aluminum chloride has been removed therefrom.

Although aluminum halides are used in the catalyst preparation according to the invention, the finished catalysts do not contain any free aluminum halide, as it is contained in the mentioned known catalysts. In making the Catalysts according to the invention will be the weight of the refractory oxide with the hydrogenation component after evaporation of the aluminum halide and heating of the mass thus formed by about 2 to about 25 ° / o. based on the original weight of the mass made of refractory oxide and hydrogenation constituent, increased. Although the exact weight gain appears to be is not critical, it has been found that highly active catalysts are obtained when the weight gain is increased in the range from about 5 to about 20%> Process for the production of halogen-containing supported catalysts

Applicant:

Universal Oil Products Company, Des Piaines, 111. (V. St. A.)

Representative: Dipl.-Ing. E. Jourdan, patent attorney, Frankfurt / M., Kronberger Str. 46

Claimed priority: V. SI. ν. America September 27, 1956

Robert Morrill Smith, Berwyn, 111. (V. St. Α.), Has been named as the inventor

lies. During the preparation and subsequent heating, the aluminum halide appears with the to react the refractory oxide containing the Tlydricr constituent. The subsequent heating treatment takes place at a temperature above that the. is required for evaporation of any Friedel-Crafts free metal halide.

The amount of ilalogenide used can be in the range from about 5 to about 50%, based on the weight of the mass of refractory oxide and hydrogenation constituent, vary. For example, if the vapor deposition is carried out discontinuously in individual batches is used, about twice as much aluminum halide is used as the weight gain in the finished mass is desired. With a continuous evaporation process, the amount can be increased one that is just slightly larger than the desired one can be reduced. Net weight gain in the finished mass. Although aluminum bromide with satisfactory results in the present process can be used, aluminum chloride is not only used because of its ease of operation Preparation of the catalysts, but also preferred because the catalysts so produced have particularly high activity.

In the starting material of refractory oxide and hydrogenation constituent used in the present process can be the refractory oxide or silica a refractory metal oxide such as aluminum oxide. Titanium dioxide, zirconium dioxide. Chromium oxide or oxvd, be. But it can also be a Mebrstoffox)

Silica-alumina, silica-magnesia, Silicic acid - aluminum oxide - magnesia, chromium oxide-aluminum oxide, aluminum oxide-boron oxide or Silica-zirconium oxide. The refractory oxide in however, the exit pinasse may be of natural origin and various degrees of purity, such as bauxite. Kaolin, Bentonittoii (the acid treated may or may not be), diatomaceous earth, such as kieselguhr or montmorillonil, or it may be a Be spinel, like magnesia alumina spinel or a zinc oxide spinel. Of those mentioned in the introduction refractory oxides, ammonium oxide is preferred; synthetically produced / alumina of a high degree of purity is particularly suitable.

The above-mentioned refractory oxides are before the attenuation of the aluminum halide * with the Hydrogenation component combined. The hydrogenation components are made from the metals of groups VI a and VJIT of the periodic table including chromium, molybdenum, tungsten. Iron, cobalt, nickel, ruthenium, Rhodium, palladium. Osmium, Iridium and Platinum selected. Of these hydrogenation ingredients is the Platinum group, especially platinum and palladium, is preferred, and platinum is preferred to palladium.

When carrying out the present process, the aluminum halide is evaporated onto the mass of refractory oxide and hydrogenation constituent at a temperature at which the aluminum halide does not decompose. In most cases, the vapor deposition is carried out at a temperature that is well above the boiling point or sublinialion point of the aluminum halide, so ■ / .. B. is not significantly more than 100 ° C higher than the boiling point or sublimation point of the aluminum halide used. In some cases, however, it may be desirable to carry out the vapor deposition step and the subsequent heating step at the same temperature.

For example, a suitable r-alumina earth may be Plalin compound placed in a glass or steel tube in a 4 "oven at the desired heating temperature and vapors of Friedel-Crafts metal halide, e.g. B. aluminum chlorides, over gelcitct will.

This particular method of catalyst production is explained in more detail in one of the examples.

The invention will be described below with reference to the more detailed description of a particular embodiment explained. As mentioned above, a particularly preferred refractory oxide for use is at the production of the desired catalysts aluminum oxide. Also preferred among the various known forms of alumina is y-alumina. aside from that the clay is preferably produced artificially and has a high degree of purity. the Methods for making such synthetic clays are well known. For example, can .she prepared by glowing aluminum oxide gel which are usually obtained by adding a suitable reagent, such as ammonium hydroxide or ammonium carbonate, to an alum in ium.-.al ζ. like aluminum chloride j Aluminum nitrate or aluminum sulphate, in a form corresponding to the formation of aluminum hydroxide Amount to be formed. The latter is converted into aluminum oxide during drying. in the generally aluminum chloride is called aluminum sal /. not only because of the convenience of the ari washing and filtering measure, also because it appears to be the best

delivers results. Alumina gels are also made by reacting sodium aluminate with a suitable acidic reagent. Synthetic clays can also be produced by the formation of aluminum oxide sols, e.g. B. by reacting metallic aluminum with hydrochloric acid. These brines can by suitable means, / .. ß. Ammonium hydroxide, with subsequent drying and annealing, can be brought to coagulate.

In another embodiment, the mass of ammonium oxide and the hydrogenation constituent can be obtained from artificially produced clays which contain about 0.01 to about 8% of bonded halogen, preferably fluorine. These clays can be halogenated in various ways, ■ / .. example by adding an appropriate amount of hydrofluoric acid can be manufactured at a alumina gel prior to drying and calcination.

Aluminum fluoride can also form aluminum oxide gels be added so as to form an aluminum oxide with the desired amount of halogen bonded therein to deliver. When the man-made aluminum oxide is prepared from aluminum chloride, it is sometimes advantageous to limit its washes to a minimum in order to achieve the desired To regulate the amount of chlorine combined with the clay.

In each of the above cases where the aluminum oxide is prepared from an alumina sol or an alumina gel, the resulting Product annealed to a temperature sufficient to convert the product to j-clay. The clays to be used in the method according to the invention can, however, also be relative Contain small amounts of water of hydration.

On the clay artificially produced in the manner set out above, the hydrogenation component is preferred a metal of the platinum group, particularly platinum, applied before being according to the invention is treated. The platinum metal, especially platinum selb.it. canoe with the clay in any one of many known ways are united. For example, an ammoniacal solution of chloroplatinic acid can be used are mixed with the clay, followed by drying. Another method can Chloroplatius acid can be added in the desired amount to an alumina yellow paste, whereupon the Platinum from it on the clay by means of hydrogen sulfide or other sulfidizing or other FäDungsmittel is precipitated. Although the amount dCi> Platinum associated with alumina is not critical, it is believed for economic reasons the amount of platinum is usually at a minimum. So large amounts of platinum do not cause any harmful effects Effects; however, about 0.01 to about 2 percent by weight of platinum, based on weight, is generally preferred on the dry clay. In another way of preparing the starting mass, you can use the clay and platinum are combined by the coprecipitation technique. In such a case it will an aqueous solution of the desired amount of platinum salt is mixed with a solution of an aluminum salt, whereupon a precipitant is added which causes co-precipitation. The resulting gel can be dried and calcined to form a supported platinum catalyst on y-alumina, which leads to the Particles of desired size can be molded.

Although the physical form of the initial mass with the refractory oxide and hydrogenation component is not critical, preference is given to c .;

generally to use macroparticles so that the finished mass can be used as a fixed bed in a reaction zone. So it is expedient to use the artificially produced clay with or without platinum in it to tablets, e.g. B. of 1.6 · 1.6 min, 5 or 3.2 · 3.2 mm size. This can easily be achieved by grinding the dried alumina gel or the dried starting material to a powder with subsequent tableting according to known methods. Instead, the particles are also present in the form of spheres or irregularly shaped particles, such as those produced when they are pressed out.

When performing the preferred embodiment According to the invention, aluminum chloride is applied to the above 1:) csch ri planar particles of alumina-platinum mass vaporized. This can easily be done by subliming the aluminum chloride onto the surface of the Particles can be achieved. Aluminum chloride sublimed at 178 ° C, and thus is a suitable evaporation temperature in the range of about 180 to about 275 ° C. Sublimation can be carried out if desired be made under pressure. The amount of aluminum chloride applied to the particles described above sublimicrt. reaches a maximum value at each selected vapor deposition temperature. In the When it evaporates on the clay platinum mass, the aluminum chloride also reacts with it to develop of hydrogen chloride. However, it is difficult to control the amount of aluminum chloride that reacts. Therefore, the mass to ensure that the resulting mass is free of aluminum chloride, then heated to a temperature above 300 ° C long enough to produce the unreacted aluminum chloride remove completely. Since aluminum chloride sublimates at J 78 ° C, the heat treatment is absent further added aluminum chloride to free the mass prepared in this way from free aluminum chloride. However, since aluminum chloride itself> I sticks to an aluminum oxide surface Temperatures as high as at least as indicated. 300 ° C required. This heat treatment can either be a further reaction of the unreacted aluminum chloride with the alumina-platinum mass or simply a sublimation of any unreacted aluminum chloride from the Create mass. During the evaporation of the aluminum chloride onto the alumina plathi mass and A certain evolution of hydrogen chloride can be observed during the subsequent heat treatment. It can be assumed that this development is due to the reaction of aluminum chloride with hydroxyl groups is based on the clay surface. This is how the first part of the aluminum chloride vapor deposited on the particles can actually exist in the form of oxyaluminum dichloride, that with free aluminum chloride is mixed on further evaporation of the aluminum chloride. Whether this assumption Applies or not, it should be left unanswered: in any case, the finished catalyst mass is free of unreacted Aluminum dichloride, and it is to be ascribed to the special sequence of process stages that the resulting finished mass has the unusual catalytic properties.

The exact temperature to use when heating the mass of refractory oxide and hydrogenation constituent onto which the aluminum halide is vapor-deposited depends primarily on the boiling point or the sublimation temperature of the substance in question used aluminum halide. In general, and especially with aluminum chloride, sine! Temperatures from about 400 to about 600 ° C and times from about 1 to about 48 hours are satisfactory. It is known that large surface areas have a favorable influence on the activity of the catalyst. In many cases these large surfaces are carefully controlled in the preparation of such carriers Conditions of warming developed at certain temperatures over certain periods of time. Therefore, care must be taken in the heating step of the method of the invention, as follows that these large surfaces are not destroyed by the aforementioned heating treatment. It is It is advantageous to carry out such heat treatments at temperatures above 700 ° C. Naturally are such temperatures related to the time while such masses of refractory oxide and hydrogenation constituent are kept at these temperatures will. In all cases, care should be taken to ensure the largest possible surface area during the subsequent To obtain heating of the catalyst mass in the method according to the invention.

This heating stage can be in the presence of various inert diluent gases can be made. Such gases include nitrogen. hydrogen and paraffin hydrocarbons, e.g. B. methane and Ethane. These gases have no harmful influence on the resulting catalyst activity. Each of the Above gases or several of them can be used as Tnlgerga.s for the aluminum halide during its evaporation as well as to create the appropriate Atmosphere can be used for the heating stage.

An unusual feature of catalysts, which have been prepared in the manner described above means that these are catalysts for reactions can be used for which it was previously considered necessary, hydrogen halide together with Friedel-Crafts aluminum halides, such as aluminum chloride. Although it should not be said that the use of hydrogen chloride with the Katalvsaturmasseu according to the invention is excluded. it has been shown that hydrogen chloride is usually superfluous in order to achieve satisfactory results. results with the finished catalyst masses -cielen. which one through the present manufacturing process receives.

As demonstrated in the examples, the process according to the invention leads to catalysts unexpectedly high activity for certain hydrocarbon conversion reactions. Such are the catalysts formed according to the process of the invention Superior masses composed of refractory oxides and Fricdel-Crafts free metal halides.

Those prepared according to the method of the invention Catalysts can be used for various with organic compounds, especially with hydrocarbons, reactions to be carried out are used). These reactions include (A) coridensation reactions, in which two molecules, which can be the same or different, form larger ones Molecules condense, (B) destructive reactions in which a molecule turns into a smaller molecule or into 2 or more molecules are broken down, (C) rearrangement reactions, e.g. B. isomerization, (D) disproportionation reactions, in which a radical is converted from one molecule into another, (E) hydrogenation reactions and (F) other reactions. First among these reactions are polymerization of Olefins, especially of ethylene, propylene,

1-butene, 2-butene, isobutylene, amylene and higher boiling olefins and mixtures thereof, secondly, alkylation of isoparaffins with olefins or other alkylating agents. like / .. B. alkyl halides, in particular the alkylation of isobutane, isopentane and / or isohexane with ethylene, propylene, 1-butene. 2-butene, isobutylene or amylene or mixtures of these, thirdly, alkylation of aromatic compounds with olefins or other alkylating agents, in particular alkylation of benzene or toluene with propylene, butylene, amylene and higher boiling points Olefins including nonenes, decenes, undecenes, dodecenes, tridecenes, tetradecenes and Pctadecenes or mixtures thereof, fourth, isomerization of paraffins, in particular of n-butane, n-peiitane, n-hexane, n-heptane or n-octane or ger.ii> ch? n 'thereof including isomerization of less highly branched saturated hydrocarbons to more highly branched saturated hydrocarbons, like the isomerization of 2- or 3-methylpentane to 2,3- and 2,2-dimethylbutane, fifth isomerization of naphthanes, e.g. B. the isomerization of methylcyclopentane to cyclohexane and the isomerization from dimethyl cyclopentane to methyl cyclohexane, subsequent alkylation of phenols or thiophenols with olefins or other alkylating agents, seventh, alkylation of thiophenes with olefins, eighth hydrogen transfer reactions, ninth alkyl transfer reactions, tenth dealkylation reactions, eleventh, reshaping of gasoline to improve the anti-knock properties, twelfth destructive hydrogenation reactions, thirteenth ^ splitting of oils heavier than gasoline into lower boiling ones Products, especially gasoline, including splitting under hydrogen pressure. and fourteenth Hydrogenation reactions in which an unsaturated compound becomes a more saturated compound is hydrogenated, e.g. B. the hydrogenation of diolefins to olefins, olefins to paraffins and of cycloolefins to naphthenes. The catalyst produced using the present process operating conditions to be used depend on the particular reaction and are in general at relatively low temperatures, although relatively high temperatures are used can, especially in reactions that are carried out approximately at atmospheric pressure. So can the Temperature in the range of 0 ° C or less to 300 ° C or more, preferably 25 to 250 ° C and the pressure can be up to 340 atm. or more, preferably 3.4 to 68 atm. If necessary or expedient, hydrogen can be used. It is believed, that hydrogen in controlled amounts plays an essential role in suppressing sludge formation and promoting many of the aforementioned responses.

The method for carrying out a reaction in the presence of one according to the present manufacturing method obtained catalyst can be made in any suitable manner, not only will depend on the particular reaction, but also on the form in which the catalyst is used will. The catalyst can be stored as a fixed bed in a reaction zone, in which he rides the introduced reaction components comes into contact. The reaction components can flow up or down through the catalyst bed be directed. The catalyst can also be used in a so-called fluidized bed process in which the catalyst is whirled up by means of the reaction components. With another Operating method can use catalyst particles of suitable size along with the reaction components flowed up and passed to a reaction zone, from which the catalyst is continuously removed and is separated from the reaction products. In each of these different modes of operation If desired, the catalyst can be activated by simultaneous Use of an ITalogenous hydrogen, such as Hydrogen chloride or hydrogen bromide, are further activated. The hydrogen halide can be used as such or in the form of a suitable organic compound, such as an alkyl halide, are supplied, from which the hydrogen halide is formed under the reaction conditions. Examples of such alkyl halides are propyl chloride, butyl chloride, allyl chloride, propyl bromide, butyl bromide and amyl bromide. The hydrogen halide can be supplied continuously or at intervals, depending on this in one the case in question is desired.

example 1

A / clay was made by dissolving aluminum tablets Prepared in hydrochloric acid to form a sol with 15 per cent. ammonium oxide. To the so) hydrofluoric acid was added, so that the finished mass 0.375 percent by weight fluorine, based on dry clay. The resulting solution was with hexamethylenetetramine in one Mixer continuously mixed and added dropwise to an oil bath at about 90 ° C to form spheres. The balls were in the oil and then in an aqueous Solution of ammonia (1 to 2 hours) ge aged. The washed balls were then put into a Transferred to dryer, dried at about 250 ° C and calcined at about 600 ° C.

A sufficient amount of the alumina spheres so produced was soaked with a dilute ammoniacal solution of chloroplatinic acid. the The amount of platinum in this solution was adjusted so that the platinum-alumina mass after drying and finished annealing (3 hours at 500 to 510 ° C) 0.375 percent by weight of platinum, based on dry Clay, contained. A sufficient amount of this platinum-alumina mass was prepared so that it was at the production of various other masses could be used.

An amount of the above-prepared mass of 50 cm ³ was placed as a fixed layer in a reaction tube and tested for its activity for the isomerization of η-butane to isobutane. The conditions used were: pressure 20.4 atm .; Molar ratio of hydrogen to hydrocarbon 0.5; Space velocity 1.01 n-butane (measured as liquid) per hour per liter of catalyst. The test was carried out at different temperatures. This mass is inactive for the isomerization of n-butane to isobutane during a 2-hour test period at temperatures of 150, 200, 250, 300 and 350 ° C. At about 400 ° C., about 1.5% isobutane appears in the product.

Example 2

Ö5 271 g of the prepared according to the information in Example 1 Platinum clay crdc mass were at in 2 hours 600 ° C, then in a glass lining in a rotary autoclave together with HOg aluminum chloride given. The autoclave was closed with J, 7Atm. Squeezed off hydrogen and

Claims (6)

9 10 Heated to 250 ° C for 2 hours and rotated. After from about 1 * / o over the temperature range from 100 to Over the course of the 2 hours, the autoclave was heated to 200 ° C. in water, but the side reactions increased submerged to ensure rapid cooling. 250 ° C to about 4%. Therefore not only will The pressure was determined from the autoclave by an equilibrium Al amount of isobutane with the hot potassium hydroxide charged scrubber drained, in wel- 5 acted catalyst at a temperature of absorbed into the evolved hydrogen chloride. 200 ° C observed, but when operating at this The amount of hydrogen chloride that was evolved will also be side reactions to a temperature reduced by back titration of the measured amount of alkali minimum, and the total yields hydroxide solution determined, which in the scrubber is increased to the desired product, had been set. This amount became 14 g of chlorine. The hot-treated catalyst was at 200 ° C ions or 0.394 equivalents of chloride. As in operation under the conditions described above this chlorine ion was developed as hydrogen chloride, in order to expand its resistance over time. Include the amount of chloride equivalents evolved. After 180 hours, its activity had reached about 0.15 per 100 g of original mass. After the 57 to 36% tsobutane in the product decreased. Autoclave was open. weighed the entire mass, free 15. . of unabsorbed aluminum chloride, 317g, what lieispicl ό an increase in weight of 17 g per 100 g of starting 112.Ig according to the information in Example 1 material revealed. platinum-clay-crdc-mass were placed in water- Hiiie amount of this mass of 50 cm ³ was reduced to the substance for 2 hours at 600 ° C and given as a fixed activity for the isomerization of η-butane under 20 layers in a glass tube under the same conditions as given above was surrounded by a vertical furnace. The bottom end of the den, namely a pressure of 20.4 atm., A mol tube was connected to a glass flask with 45 g of anhydrous ratio of hydrogen to hydrocarbon equal to aluminum chloride. The temperature of the 0.5. Hourly liquid hourly space velocity platinum-clayey mass was set at 600 ° C; of 1.0 and tested at different temperatures, as the glass flask with the aluminum chloride was heated at 100 ° C less than 1% isobutane in the preheat until it began to sublime. A nitrogen duct observed, about 6% tsobutane at 150 ° C. In the case of a gas flow, about 27.5% isobutane was then introduced into the glass flask through a gas inlet tube at 200 ° C. and 50% isobutane at 250 ° C. in order to remove the alubutane. So the mass is an active isomerization! «- mini-dichloride vapors through the platinum-alumina mass catalyst. 30 upwards, which was kept at 600 ° C. Another sample in the amount of 58.5 g of the above. This was continued for 3.5 hours, after which aluminum wrote Mass of platinum and alumina with darminium chloride vapors at the exit end or at the on sublimed aluminum chloride was placed in a tip of the glass tube of the platinum-clay-crdc-mass-glass tube given that were respected by a horizontal furnace. At the end of 3.5 hours the was surrounded and heated to 315 ° C. In addition, the passage of aluminum chloride into the tube with the 35 At this temperature for 17 hours nitrogen was broken off mass, and the mass was then diverted. This temperature of 315 ° C is left well above cool and weighed on it. It was found half the sublimation temperature of aluminum - an increase in weight corresponding to 6.7 g per 100 g of uric chloride. namely 178 ° C. During these 17 hours of spring platinum-alumina mass. This preparation at 315 ° C the mass lost 2.17 g of chloride, determined * o explains a process for the production of these active substances as hydrogen chloride. The lYlasse was then again a catalyst, in which both the initial vapor Heated to 520 ° C in a nitrogen stream and the aluminum halide acted on the mass as Maintained at this temperature for 1.5 hours, during which the heating of the mass at the same temperature again chloride in an amount of 0.84 g. must be carried out on site. true than hydrogen chloride, lost. The total net 45 50 cm ^{4 of} the mass produced in this way were calculated on weight gain as a result of this different merization of η-butane among those described above Steps was about 12 g per 100 g of the original conditions, namely 20.4 atm. Pressure, 0.5 molar Platinum-alumina mass compared to the 17 g per ratio of hydrogen to hydrocarbon, 1.0 hour 100 g given above. borrowed liquid space velocity and at different The temperatures thus different according to the method according to the invention 50 were tested. At 100 ° C were The catalyst produced was then observed for the tsomeri 7.6% isobutane in the product, at 150 ° C η-butane at a pressure of 20.4 atm., 40.8 "/" and at 200 ° C 56.0%. Here the process a molar ratio of hydrogen to carbons according to the invention in turn for production hydrogen equal to 0.5 of an hourly liquid * - a highly active conversion catalyst. In order to space velocity of 1.0 and at various 55 has been shown to be a highly active catalyst for Temperatures needed. At 150 ° C the isomerization of saturated hydrocarbon 28% isobutane in the product, at 175 ^e C 48% and fen using aluminum halide manufacturer 200 ° C 57%. It is thus evident that the procedure can be established, but without the need to Ren according to the invention to add very active catalysts when using hydrogen chloride, for the isomerization of saturated hydrocarbons 60 substances, they are actually more active than the ahn patent claims: borrowed catalyst that was not treated with heat. 1. Process for the production of a halogen-containing Here again, as in the previous term supported catalyst, characterized Test series the tests in the absence of too- that one aluminum halide on one before set hydrogen chloride carried out. 65 mass prepared in a known manner, consisting of The advantage of the method according to the invention is from a refractory oxide as a carrier and a further explained by examining the side reaction metal active in hydrogenation reactions tion that occurs at different temperatures. Also groups VIa and VIII of the periodic probably with the hot treated as with the not system, vaporized and then the so hot treated catalyst, side reactions occurred 70 acted mass to a temperature above Heated to 300 ° C until practically everything has not reacted Aluminum halide has been removed therefrom. 2. The method according to claim 1, characterized in that the aluminum halide is evaporated onto a mass which consists of a refractory metal oxide and a metal of the platinum group, and unreacted aluminum halide from the resulting mass by heating to a temperature between 30O ¹ and 700 ° C is removed. ίο 3. The method according to claim 2. draws that aluminum chloride is evaporated onto a mass that consists of alumina and platinum, and the resulting mass is heated to a temperature in the range from 400 to 600 ° C. 4. The method according to claim 1, characterized in that the aluminum halide on the A mass of refractory oxide and metal is evaporated in such an amount that after removal the unreacted aluminum halide from the mass by heating to over 300 ° C the weight of the resulting mass is about 2 to about 25% greater than that of the Procedure supplied mass. 5. The method according to claim 2 or 3, characterized in that the aluminum halide in of such an amount to a mass consisting largely of alumina and of platinum in an amount of 0.01 to 2% and bound fluorine in an amount of 0.01 to 8% by weight of the clay, is evaporated that after removal of the unreacted aluminum halide from the Mass by heating to over 300 ° C the weight of the resulting mass about 5 to about 20%> is greater than that of the mass fed to the process. 6. The method according to any one of claims 1 to 5, characterized in that the vapor deposition of Aluminum halide and the removal of unreacted aluminum halides at the same time by heating the starting mass to about 300 ° C in contact with a stream of inert gas, the loaded with the aluminum halide is carried out. © 809 730/415 1.59