DE1922755A1 - Process for the preparation of dimerized saturated ketones - Google Patents

Description

Process for the preparation of dimerized saturated ketones Die The invention relates to a process for the preparation of dimerized saturated ketones in more selective with se from ketones and hydrogen. In particular, the invention relates a process for the reaction of ketones and hydrogen using an im essentially of metallic palladium and a phosphate of at least one of the Metals zirconium, titanium, hafnium and tin existing catalyst, being in one Stage the dimeric condensation and hydrogenation of the ketones is achieved and thereby Saturated ketones are formed which are due to the condensation of two molecules and which are hereinafter referred to as dimerized saturated ketones will.

The term ketones is usually the general name for such organic compounds, Uie is one given by the formula> C = O Atomic group, i.e.

the carbonyl group. However, the ketones are useful in accordance with the invention can be used, limited to those that are condensable. Consequently can the condensation and saturation conversion between those in the following groups (a) or (b) specified ketone molecules be performed. To The present invention enables (a) the dimeric tone densation and saturation conversion perform between ketone molecules in which at least one hydrogen atom to one or both of the two carbon atoms attached to the carbonyl group is bonded and hereinafter referred to as carbon atoms in the α-position and (b) the condensation and saturation conversion between a ketone molecule, wherein two or more hydrogen atoms on either or both of the carbon atoms the α-position are bound, and carry out a ketone molecule that does not have any Has hydrogen atoms on the carbon atoms of the a-position.

Unless otherwise stated, the one used here denotes The term "ketones" means the condensables listed above under (a) and (b) Ketones.

As a process for the production of saturated ketones, initially dimerizing the ketones were condensed and then the hydrogenation of the same was carried out, i.e. a process for the preparation of the above as dimerized saturated ketones according to the invention designated compounds, it was previously customary first carry out the condensation reaction of the ketones using an alkali, then the ketol obtained with subsequent dehydration with the formation of to narrow unsaturated ketones, in which the above ketones dimerizing were condensed, and then these unsaturated ketones of a hydrogenation stage to subject, whereby the dimerized saturated ketones were obtained. at in addition to the fact that the work stages were complicated, also the disadvantages that the yield due to the relative low Conversion during the condensation step was low and that substantial amounts des carbinols were formed as a by-product during the hydrogenation step.

Furthermore, a method has been proposed, wherein the dimerized unsaturated ketones by direct condensation of two molecules of the ketones under Application of a molecular sieve as a catalyst were formed and then the unsaturated ketones obtained were subjected to the hydrogenation step. This Process has the disadvantages that not only the catalyst activity of the molecular sieves is insufficient, but that the decrease in the activity of the catalysts in Passage of time is great. It is also necessary to carry out the hydrogenation reaction perform as a separate step after the dimerized unsaturated ketones were obtained.

It is an object of the invention to provide a method by which the dimerized saturated ketones from the starting material in good yield and economical can advantageously be obtained in a one-step reaction process.

Another object is a process for making dimerized ones saturated ketones selectively from the starting ketones in good yield in a one-step Reaction procedure.

Another object is a method for producing Methyl isobutyl ketone by a one-step reaction process by condensation and saturation of two molecules Ace @@@@@ Another object of the invention is in new catalysts, by means of which the dimeric condensation and hydrogenation conversion of ketones can be carried out in one step.

Another object of the invention is a method for Production of the new catalysts, the activity of which offered particularly high performance the dimeric condensation and hydrogenation reaction of the ketones.

Other objects and advantages of the present invention will emerge from the description below.

The ii framework of the invention to be used catalyst consists of a catalyst system, which meta cal palladium and a phosphate at least contains one of the metals ziconium, titanium, hafnium or tin. Below is a Description of the individual components brewed that make up the catalyst of the invention form and the manufacturing process of the catalysts from this component @@ described.

The metal phosphates The metal phosphates to be used in the context of the invention are made by reacting phosphoric acid with one or more water-soluble ones Salts of zirconium, titanium, hafnium or tin and isolation of the obtained Precipitation received. Since the above implementation is a reaction between the represents the above metals (M) and phosphate ions (PO4-3) in an aqueous medium, the phosphoric acid does not necessarily have to consist of phosphoric acid itself, but can be any compound that contains the phosphate ions (PO4-3) in one aqueous medium supplies. Examples are the neutral and acidic ones Salts of phosphoric acid including those of sodium, galium, lithium and ammonium, and dis acidic salts of phosphoric acid including those of magnesium and calcium, as well as other water-soluble Phosphates. Of these, phosphoric acid and the acidic salts of phosphoric acid are preferred, in particular However, phosphoric acid on the other hand can be used as water-soluble salts of zirconium, Titans, hafniums and tin are all used to provide these metal ions however, particularly preferred are the halides, oxyhalides, oxynitrates and Oxysulphates of these metals.

All known methods for implementing one or more of the water-soluble salts of zirconium, titanium, hafnium and tin with the phosphate ions in an aqueous medium for the production of zirconium, titanium, hafnium or tin-IV phosphate can be applied. For example, all of the methods according to J. Inorg. and Nucl.

Chem., Volume 6, pages 220-235 (1958) and Volume 26, pages 117-129 (1964) and Volume 28, pages 607-613 (1966) can be used.

Since the molar ratio PO -3 / M @ of the above phosphate ions (PO4-3) to metal (Me) is not particularly limited and each of the components can be applied in a large amount is generally an area in which one the part. does not exceed three times the molar amount of the other of Favorable in terms of economy. As an example of the most preferred embodiment becomes a water-soluble salt of at least one of the metals zirconium, titanium, hafnium or tin with either phosphorous acid or a water soluble salt thereof in a molar ratio of phosphate ions PO4-3 to the above metal ions (Me), i.e. a molar ratio PO4-3 / Me in the range from 0.6 to 1.7. In this Case will get particularly good results obtained as metal phosphates with a large specific surface can be obtained. In this case it is particularly favorable that the precipitation of the above metal phosphates from a Low concentration solution occurs. Particular favorable results will be obtained when this precipitate is dried without heating.

Furthermore, the metal phosphates, which by drying the gel-like Precipitation was obtained, which by reaction of the water-soluble salts of the above metals lit with the phosphate ions PO4 @@ in an aqueous solution a pH word of 3 or more and pH 12 or less as a precaution, also have a particularly large specific surface and can therefore favorably be used. In this case it is possible as there are no particular restrictions with regard to the molar ratio PO4-3 / Me of phosphate ion PO4-3 to metal (Me) consist of facing each of the ingredients in a substantial excess amount the other to use, To adjust the pH of the reaction system 3 to 12, the following procedures are preferred in this case: 1.) You method of adding a strong alkali to the reaction system, for example Caustic alkalis, caustic alkalis and alkali carbonates and 2.) the method of addition of ammonia to the reaction system.

In the case of the above method (1), however, the tendency occurs on that some of the metal phosphates obtained by alkali or alkaline earth metal ions is substituted.

On the other hand, when the above method (2) is used, irt some of the metal phosphates obtained are substituted by ammonium ions. That's why it will if by setting the pH value according to the above Process (1) and (2) obtained metal phosphates for the catalysts according to the invention processed by mixing with the metallic palladium described below are preferred that the above metal phosphates in the acid type by further Treatment to be converted, The conversion of these metal phosphates to the acid type is not subject to any special restrictions and ea can all of the to sioh known methods are used. Usually the conversion can sum acid type can be achieved in the following way: In the case of the above method (1) the precipitate obtained after completion of the reaction is treated with an acid, whereby the hydrogen atoms are the partially substituting alkali or alkaline earth ions substitute, while in the case of the above method (2) that after completion the reaction obtained precipitate is dried by heating, for example to 300 to 600F, which decomposes and removes the ammonia.

Metallic palladium With regard to that which can be used in the context of the invention metallic palladium, there are no particular restrictions and usually The metallic pallamium, for example palladium black, can be all of these or one Palladium carried on a carrier can be used, which is available from A @ @ingen of water-soluble palladium salts, for example palladium sulfate, palladium nitrate or palladium halides, on an inert support and then carried out a reduction treatment.

Preparation of the catalyst Those which can be used in the context of the invention Catalysts can be prepared in any way provided that they have the components listed above metallic palladium and a phosphate of Contains zircon, titanium, hafnium or tin. For example, those for which the phosphates of the above metals and the metallic palladium prepared separately and which are either blended as received or blended after each of the ingredients is on an inert support, for example Diatomaceous earth, aluminum oxide, silica, activated carbon or clay was applied or those in which the metallic palladium is based on the phosphates of the above Metals is worn, for example by common precipitation or after Ion exchange process, the so-called bifunctional len catalysts orhalten which are then either in the retained state or after further application the above inert carriers are used. The process for manufacturing the catalysts are therefore not subject to any particular restriction. Furthermore you can the catalysts according to the invention are used either in powder form or in granular form will.

although all of the processes known per se for production of the bifunctional catalysts consisting of metallic on the above Metallphoaphaten are made of palladium carried, can be used Conveniently, for example (1) a method wherein a water-soluble palladium salt to the system during the reaction to produce the above metal phosphates is added and dissolved therein, whereupon the moisture content evaporated and is removed and then the palladium salt carried on the phosphate is subjected to a reduction treatment, (2) a method wherein the preformed Metal phosphates immersed in an aqueous solution of a water-soluble palladium salt are, ansohllessend the moisture content is evaporated and removed and then the palladium salt carried on the phosphate is subjected to a reduction treatment and (3) a method wherein palladium ions are converted into the cationic by ion exchange Ion exchange group of the metal phosphates are introduced and then the Reduction treatment is carried out, applied. The near this procedure (1), (2) and (3) obtained catalysts according to the invention show a catalytic activity, which dominates that of the catalysts, which only by mixing the the above xetallphosphate with metallic palladium were obtained.

When the catalysts according to the procedure described above (1), (2) and (3) and in particular after the method (5) were obtained excellent catalysts obtained in which the metallic palladium is uniform and is deposited in a very finely divided state.

The process of introducing the palladium ions through ion exchange in the cationic exchange group of the metal phosphates is not subject to any special ones Limitations, however, are usually imposed by adjusting the pH of the solution durohführung that the water-soluble palladium in the manufacture of the above contains bifunctional catalyst. When the palladium was introduced.

as ions in the cationic exchange groups of the metal phosphates it is preferred to use substances which through implementation Cation-like ions of palladium in aqueous solution that are stable with the palladium salt form. Such substances are usually ammonium hydroxide and water-soluble ones organic amines such as methylamine and ethylamine are favorable. Have these connections the advantage that they react with the palladium salts and the palladium in stable Transfer water-soluble complex cations and the pH of the reaction solution at the same time regulate, so that the ion exchange of the palladium cations with the Cations of the metal phosphate is easily effected.

Especially in the case where the palladium salt is in the form of palladium tetrammine complex ions [Pd (NH3) 4] 2+ is introduced and the ion exchange of the complex ions with the kaionic Exchange group of the above metal phosphates using ammonium hydroxide this procedure is usually the most effective.

If the pH of the solution is 3 to 12 and preferably 4 to 7 when performing the ion exchange between palladium ions and the cationic The exchange group of the metal phosphates is retained, the ion exchange takes place of the palladium ions preferably regardless of the concentration of the palladium ions. On the other hand, when the pH of the solution is less than 3, i.e., a condition at where the hydrogen ion concentration is large. the ion exchange proceeds Hydrogen ions to the cationic exchange group of the metal phosphates, either the introduction of the palladium ions or the palladium is inhibited remains impregnated in the form of a palladium salt. Compared to a catalytic converter, which was produced in a pH range specified above is a catalyst, made with a solution with a pH below 3 became, in terms of its selectivity for the intended dimerized saturated retone something chlochter. If the pH of the above containing palladium Solution is greater than 12, the palladium is not completely introduced as ions, with the result that the selectivity for dimerized saturated ketones of the obtained Catalyst in this case also gets a little worse.

As a method of introducing the palladium ions into the cation exchange group the zirconium, titanium, hafnium or tin phosphate is usually used to advantage either the simultaneous ion exchange method in which the palladium cations by ion exchange during the production of the above metal phosphates introduced, or the sequential ion exchange method applied, in which the palladium cations in di.

Cation exchange group of metal phosphates are introduced after these metal phosphates were obtained.

The catalyst obtained by the simultaneous ion exchange method is particularly effective when used as a catalyst in the present invention will.

The simultaneous ion exchange method is carried out in the following way: For example, a palladium salt is first dissolved in an aqueous one or more water-soluble Solution containing salts of zirconium, titanium, hafnium and tin dissolved. Then it will be this aqueous solution with either phosphoric acid or a water-soluble phosphate with the simultaneous presence of a stable palladium cation in the aqueous solution by reaction with the Palladiuiealz-enabled substance (hereinafter referred to as a palladium-forming agent ), e.g. ammonium hydroxide, reacted while the pH of the reaction solution was kept in the range of 3 to 12 is, and in this way a hydrogel of the metal phosphate is produced by the Ion exchange with palladium cations has taken place, and then the hydrogel filtered off. The palladium cation forming agent listed above can be used to the phosphoric acid or the aqueous phosphate solution are added beforehand, or it can be added to the solution after the formation of the aforementioned hydrogel will.

On the other hand, the sequential ion exchange method appears Carried out in the following way: Zirconium, titanium, hafnium prepared in advance or tin phosphate is immersed in a solution containing stable palladium cations contains, e.g. [PdA4] ++, where A is NH3, CH3NY2 or C2H5NH2, and the ion exchange takes place in a standstill state, or the metal phosphate standing before is in packed into a column through which a solution containing the palladium cations is passed with the ion exchange occurring in an optimal manner. Then will the metal phosphate containing the exchanged ions was thoroughly washed with water. In this way the metal phosphate is obtained by the ion exchange with palladium cations was effected.

So there is no restriction on the palladium compound, to carry out the ion exchange of the cationic exchange group of above metal phosphates is to be used as long as the palladium compound in can deliver palladium ions to an aqueous medium. Usually the water soluble ones Palladium salts such as palladium sulfate, palladium nitrate and Palladium halides, suitably used.

The phosphates of at least one of the metals zirconium, titanium, hafnium or tin obtained as described above or by other known methods and into which palladium cations were introduced by means of ion exchange processes are then subjected to a reducing treatment to to convert the palladium cations into metallic palladium. The metal phosphates can therefore be converted into their acid form and at the same time the metal phosphates metallic palladium applied evenly and in a very finely divided state will. According to the ion exchange method described above, the palladium becomes on the metal phosphates given above as very finely divided metallic palladium applied with a particle diameter of not more than 100 #.

Regarding the reduction treatment to be used according to the invention as specified above include, for example, the calcination of the metal phosphates obtained after ion exchange in a stream of hydrogen at 100 to 600 ° C and preferably 300 to 500 ° C; the Process in which first calcination is carried out in air at 200 to 500 ° C, and then the reduction in a reducing atmosphere, for example a hydrogen stream and the method in which the reduction treatment is carried out using known reducing agents such as formaldehyde, formic acid, sodium borohydride and hydrazine, and then the metal phosphate of an acid treatment is subjected to the ammonium ion in those cases where the above reducing agents applied were to remove.

The amount of the metallic contained in the catalyst according to the invention Palladium is expediently between 0.1 and 6.0% by weight and in particular between 0.2 and 3.0% by weight, based on the metal phosphate. Wnn the content of metallic Palladium is below the range given above, take the by-products predominantly the trimeric condensation products of the starting ketone, to, while, if the palladium content exceeds the above range is also undesirable is because the formation of carbinol sunint easily.

The site of activity responsible for the dimerized condensation reaction (hereinafter referred to as simple condensation) of ketones in the case of the invention The catalyst used is effective is the acid ion exchanging group of the phosphates one or more metals consisting of zirconium, titanium, hafnium or tin, while as a site of activity that is responsible for the hydrogenation of those produced by condensation In dimerized and saturated ketones, metallic palladium is believed to be effective will.

Reaction conditions Although the reaction conditions to achieve dimerized saturated ketones by reacting the ketones depending on the one used Starting ketones and the type of reactor used in the invention may vary somewhat in general, a reaction temperature of 60 to 400 ° C and favorable preferably 80 to 250 ° C, a reaction pressure of 1 to 50 kg / cm², and preferably 1 to 30 kg / cm², and a molar ratio of hydrogen to ketones, i.e.

Hydrogen / ketones in the range from 0.01 to 2.0 and preferably 0.1 to 1.0 can be used, but the above conditions are not necessarily limited to these areas.

Furthermore, the starting ketones can under the reaction conditions a Represent the liquid or vapor phase, but there is a tendency to increase the formation various hub products, of which the trimerized condensation product predominates, exists when the ketones have been reacted while they are kept in the vapor phase it is usually advantageous in most cases to carry out the reaction while the ketones are kept in a liquid phase. In this case, i.e., if the reaction is allowed to proceed while the ketones are in a liquid phase are held, good results are generally obtained if, for example the liquid hourly space velocity of the ketones in a range of 1 to 20 (liquid volume / catalyst volume / hour), although also one.

lower or higher speed outside of the above Area can be used.

In the process according to the invention, the formation of by-products, in particular the formation of carbinol, due to the reaction temperature and the molar ratio from hydrogen to the starting ketones and in particular influenced by the latter. Suitable conditions should therefore be chosen depending on the starting ketones been.

The influence of the reaction pressure on the formation of by-products however, it is small compared to the influence of the hydrogen / ketone molar ratio.

The type of reaction to be used according to the invention and the reaction device are not particularly limited, and known reaction methods can be used and reaction devices can be used without modification.

That means either batch or continuous processes can be used can be applied, and in the case of the continuous process, either the known reaction processes and reaction devices with a fixed catalyst bed, Fluidized bed catalyst or the fluidized bed used in hydrogenation, can be used without modification.

Ketones According to the process according to the invention, (a) the dimeric condensation and Saturation reaction between K @ clay molecules can be carried out in which at least ei @ hydrogen atom either on one or on both carbon atoms of the α-position, associated with the carbonyl group is bonded and (b) the dimers Condensation and saturation reaction between a ketone molecule in which at least two hydrogen atoms on either or both of the aforementioned carbon atoms the α-position are bound and a ketone molecule that does not contain hydrogena @ om having bonded to the carbon atoms of the α-position.

Ketones falling under (a) include any retone of the following formula: in which R1 is an alkyl, cycloalkyl, aryl, aralkyl, alkaryl or alkenyl radical and R2 and R3, which can be identical or different, are each hydrogen, an alkyl, cycloalkyl, aryl, aralkyl, alkaryl or alkenyl radical, and those ketones in which the total sum of carbon atoms is 3 to 19 are suitably used.

In process (b) above, the dimeric condensation and Saturation reaction between the ketones belonging to (a), but in which at least one of the radicals R2 or R3 denoted a hydrogen atom and / or in which at least a few two hydrogen atoms to the carbon atom of the α-position in the radical R1, the is linked to the carbonyl group, and a ketone that no hydrogen atom at all on carbon atoms in the a-position, those with the carbonyl group are linked, has bound, such as diphenyl ketone and di-tert-butyl ketone.

According to the present invention, the dimers can be condensed and saturated ketones (dimerized saturated ketones) have any limitation with regard to the ketone molecules defined in (a) and (b), however the reaction is to achieve the dimeric condensation and saturation between the ketones in good yields, preferably between ketones of a single class carried out as a variety of product classes are formed when the reaction is carried out with a ketone mixture of different classes, which has the consequence, that the separation becomes complicated.

For specific examples of these which can be used in the process according to the invention Hetones include acetone, methyl ethyl ketone, Diethyl ketone, methyl propyl ketone, Methyl isobutyl ketone, ethyl hexyl ketone, dinonyl ketone, acetophenone, methyl cyclohexyl ketone, Isopropyl tert-butyl ketone and isopropyl phenyl ketone. In the following table I Typical products are listed that result from the use of these ketones.

Table I starting ketone main reaction product 1 acetone methyl isobutyl ketone 2 methyl ethyl ketone 3-methylheptan-5-one 3 diethyl ketone 3-ethyl-4-methylheptan-5-one 4 methyl propyl ketone, 4-methylnonan-6-one. 5 methyl isobutyl ketone, 2,6,8-trimethylnonan-4-one 6 ethyl hexyl ketone 7-ethyl-8-methylpentadecan-9-one 7 dinonyl ketone 11-octyl-12-nonyleneicosan-10-one 8 acetophenone 8-phenyl-propylpropyl ketone 9 methylcyclohexyl ketone 2,4-dicyclohexylbutan-4-one 10 isopropyl tert-butyl ketone 2,2,4,4,6,6-hexamethyl-3-isopropylheptan-5-one 11 isopropylphenyl ketone 2,4,4-trimethyl-3,5-diphenylpentan-5-one 12 # acetone 2-methylhexan-4-one # methyl ethyl ketone 13 # acetone 1,1-diphenylbutan-3-one # diphenyl ketone 14 # acetone 2,2-dimethyl-3-isobutylhe- # di-tert-butyl ketone xan-5-one 15 # methyl isobutyl ketone 1,1-diphenyl-5-methylhexane # diphenyl ketone 5-one 16 # acetone Dii @ obutylketon #Methylisobutylketon The following examples serve for a more detailed explanation of the invention to restrict chne @ie. The determination of the Dimerized saturated ketones obtained as the product were carried out by gas chromatography. On the other hand, the palladium content of the catalyst was determined by fluorescent X-ray analysis bestlist.

Examples 1 to 8 of the examples given serve to illustrate the various methods for preparing the catalyst according to the invention under Application of ion exchange technology.

Example 1 The various listed under Nos. 1 to 13 of Table II water-soluble metal salts were dissolved in water and then the various water-soluble palladium salts indicated under No. 1 to 13 of the table Heating dissolved. The phosphoric acid components listed in Table II were separately dissolved in water. At first, the first mentioned solution slowly became too added to the last-mentioned solution at room temperature with stirring, after which ammonia water (concentrated ammonia water, unless otherwise stated) was added until the pH indicated in Table II was reached. Then the solution fortgeset @ t stirred for 4 hours, and then left quiet for 24 hours stand. The resulting precipitate was filtered off, washed with water and after Remove the remaining unsettled portion of the above salts at 110 ° C, the gel-like metal phesphates listed in Table II @ were obtained that were partially substituted with palladium cations. The so obtained gel-like products were cut to a grain size of 2.4 to 1.7 mm (8 to 12 mesh JIS Z8801) pulverized, after which it was placed in a stream of hydrogen at 400 ° C 8 hours were calcined and thereby the desired catalysts were obtained.

Table II Catalyst Ingredients Metal used as the phosphoric acid ingredient Palladium as no. Class added - water class added - water class added to level to level amount dissolve amount dissolve amount (g) sen (l) (g) sen (l) (g) 1 ZrOCl2.8H2O 97 6 H3PO4 70 6 PdCl2 0.71 2 "97 6" 35 6 "0.50 3" 97 2 "70 2" 0.71 4 "97 2 "70 2" 1.4 5 "97 6 NaH2PO4.2H2O 56 6" 0.50 6 "97 6 H3PO4 70 6 Pd (NO3) 2 0.92 7 "97 6" 70 6 PdSO4.2H2O 0.96 8 "97 6" 70 6 PdCl2 0.28 9 "97 6" 70 6 "1.42 10 "97 6" 70 6 "2.15 11 TiCl4 57 5" 70 5 "0.80 12 HfOCl2.8H2O 41 3" 24 3 " 0.3 13 SnCl4.5H2O 100 6 NaH2PO4.2H2O 112 6 "0.8 Table II (continued) Catalyst Preparation Conditions Catalyst Received No. Compound Molar Ratio pH value of the class Pd content sur Finstel- nis reaction (% by weight) development of the (PO4-3 / Me) solution pH value (ml) 1 NH4OH 72 2.1 5.0 Zirconium phosphate 0.5 2 "60 1.0 4.8" 0.5 3 "90 2.0 7.6" 0.5 4 "90 2.0 4.0" 0.5 5 1N NaOH 1.0 5.0 "0.5 6 NH4OH 2.0 5.0 "0.5 7" 2.0 5.0 "0.5 8" 2.0 5.0 "0.2 9" 2.0 5.0 "1.0 10" 2.0 5, 0 "1.5 11 "2.0 5.0 titanium phosphate 0.8 12 1N NaOH 2.0 5.0 hafnium phosphate 0.4 13" 2.0 5.0 Tin phosphate 0.5 In experiments 1 and 3 in Table II was To adjust the pH value, ammonia water was added in amounts of 7.2 or 90 ml. On the other hand, in Experiment No. 2, 60 ml of ammonia water were used to adjust the pH added immediately after dilution of the phosphoric acid with water and then added to Preparation of the catalyst mixed with an aqueous zirconium oxychloride solution.

Example 2 After dissolving 97 g of zirconium oxychloride (ZrOCl2.8H2O) 0.71 g of palladium chloride were dissolved in 6 l of water with heating. on the other hand 70 g of phosphoric acid were diluted with 6 l of water. The former solution then became added to the latter with stirring at room temperature, after which the pH of the Reaction solution by adding 40% aqueous methylamine solution under continuous Stirring was stopped. The molar ratio PO4-3 / Zr at this point in time was 2.0. Stirring was then continued for a further 4 hours, after which time the reaction solution was allowed to pierce for 24 hours. The obtained precipitate became then filtered off, washed with water and dried at 110.degree. After that, the Precipitate pulverized to a particle size of 2.4 to 1.7 mm (8 to 12 mesh JIS) and calcined at 300 ° C. for 3 hours in air. Then the calcined Product for 6 hours at 400 ° C in a hydrogen stream of a reducing Subjected to treatment, and a zirconium phosphate catalyst was obtained, its Palladium content was 0.5% by weight.

Example 3 Dried gel obtained when carrying out the method was obtained under identical conditions as in Experiment 2 of Example 1, was pulverized to a particle size of 2.4 to 1.7 mm (8-12 mesh) and then for 4 hours at 100 ° C a reducing treatment using Subject to formaldehyde vapor.

The gel was then treated with 0.1N HCl for 24 hours at room temperature impregnated in order to remove the ammonium ions then with water until it is free of chlorine ions washed and then dried at 110 ° C, using a zirconium phosphate catalyst with a palladium content of 0.5 wt .-% was obtained.

Example 4 (1) 35 g of phosphoric acid were diluted with 3 liters of water. On the other hand, 97 g of zirconium oxychloride was dissolved in 3 liters of water. The two solutions were then reacted with stirring by taking them at a constant rate Use of a constant flow pump for a period of approximately Into a reaction tank kept at a temperature of 40 ° C. dropwise for 3 hours were introduced. The pH of the reaction solution was 1.0 and the molar ratio PO4-3 / Zr in this case was 1. The precipitate obtained was after one had left him standing for about 24 hours, repeatedly washed with water until his pH 3 reached. The precipitate was then filtered off, dried at 110 ° C, and the product obtained was zirconium phosphate.

(2) After pulverizing the above zirconium phosphate to a Particle sizes from 2.4 to 1.7 mm (8-12 mesh) were placed in a glass column of 15 ml packed, after which 1 1 0, 1N ammonia water containing 2 g of palladium chloride, for Implementation of the ion exchange reaction was passed through the glass column. then the zirconium phosphate present after ion exchange was washed thoroughly with water washed and after pre-drying at 110 ° C in a Wa.serstoffstrom during Reduced 8 hours at 400 ° C while sucking ammonia gas, and obtained zirconium phosphate, the palladium content of which was 2.0% by weight.

Example 5 23.2 g of sodium hydroxide were dissolved in 3 liters of water, then 48 g of phosphoric acid were added, 64.4 g of zirconium oxychloride, likewise with vigorous stirring in solution in 3 l of water were added. The pH of the aqueous solution was below at this point it was 3.8 and the molar ratio PO4-3 / Zr was 2.0. The received gel-like precipitate became after being left to stand for about 24 hours, filtered off, washed with water and dried at 110.degree. The dried precipitate was then treated with 0.1N HCl, washed with water to remove the chlorine ions, dried at 110 ° C and then the gel-like product obtained on a Particle size from 76 to 53 µ (200-300 mesh) comminuted. Separated was 0.45 g of palladium chloride dissolved in 10 ml of 28% ammonia water and then with 200 ml of water diluted. 50 g of the dried gel-like product obtained above were then immersed in this solution and during 24 hours left to stand at room temperature.

The procedure was then continued as in Example 4, with zirconium phosphate with a content of 0.5 wt .-% palladium was obtained.

Example 6 57 g of titanium tetrachloride were dissolved in 100 ml of 35% HCl solution dissolved and then diluted with 5 liters of water. On the other hand, there was 70 g of phosphoric acid diluted with 5 liters of water. The two solutions were then taken at room temperature Stir mixed, after which the pH of the reaction solution by slowly pulling @ be from 28% ammonia water was adjusted to 5.0. After continued stirring during The solution was allowed to stab for a further 4 hours. The molar ratio PO4-3 / Ti was 2.0 at this point in time. After that, processing as in example 5 obtained a titanium phosphate catalyst with a palladium content of 0.5% by weight.

Bciiiel 7 24 g phosphoric acid and 12 g caustic soda were in 500 ml Dissolved in water. Separately, 41 g of hafnium oxychloride was dissolved in 500 ml of water. the The latter solution was then mixed and mixed with the former solution at room temperature implemented. The pH of the reaction solution at this point was 5.0, and that The molar ratio PO4-3 / Hf was 2.0. Then as in Example 5 was continued worked, and @inen hafnium phosphate catalyst was obtained with a palladium content of 0.5% by weight.

Example 8 (IV) -210 g of tin chloride were dissolved in 600 μl of water.

187 g of sodium dihydrogen phosphate were separated in 1.2 l of 1,2N sodium hydroxide solution solved. The former solution then quickly became subordinate to the latter at room temperature Stirring added. The resulting precipitate was filtered off and washed with water, until the pH reached 3.2. The pH of the reaction solution was at the time of the preparation of the catalyst at 2.0, and the molar ratio PO4-3 / Sn was ~ 2. Thereafter, during further processing as in Example 5, tin phosphate with a palladium content was obtained of 0.5 wt .-% obtained.

Example 9 Dimerization and Saturation Reaction of Acetone The in Catalysts obtained from Examples 1 to 8 were used, and methyl isobutyl ketone (hereinafter abbreviated to MIBK) was made from acetone. 15 ml (about 15 g) each of the catalysts listed in Table III were in the middle part of a Reaction tubes 35 cm long and 20 mm in diameter packed in stainless steel. If the reaction of the acetone in the presence of hydrogen is below the limits given in Table III The specified reaction conditions carried out are those given below Get results. The pressure in all cases was the gauge pressure (kg / cm²) measured at the outlet end of the reaction tube. apart from the abbreviations used in Table III from MIBK, were IPA and DIBK, which mean isopropanol and di @ obutyl ketone, respectively.

Table III Catalyst Used Reaction Conditions No. Class Palladium example amount of water temperature pressure content no. (° C) (kg / cm²) (% by weight) Conducted amount of ketone (l / h) (ml / h) 1 zirconium phosphate 0.5 1 (No.1) 60 3 110 5.5 2 Zirconium Phosphate 0.5 1 (No.2) 60 4 108 5.6 3 Zirconium Phosphate 0.5 1 (No.3) 30 6 120 5.6 4 Zirconium Phosphate 0.5 1 (No.4) 30 5 120 6.1 5 Zirconium Phosphate 0.5 2 60 3 110 5.5 6 Zirconium Phosphate 0.5 1 (# 5) 60 4 108 5.6 7 Zirconium Phosphate 0.5 1 (No. 6) 60 3 110 5.5 8 Zirconium phosphate 0.5 1 (No. 7) 60 3 110 5.5 9 Zirconium phosphate 0.2 1 (No.8) 60 4 112 6.2 10 Zirconium Phosphate 1.0 1 (No.9) 60 4 112 6.2 11 Zirconium Phosphate 1.5 1 (# 10) 60 4 112 6.2 12 Zirconium Phosphate 0.5 3 60 4 108 5.6 13 Titanium Phosphate 0.8 1 (# 11) 30 3 120 6.1 14 hafnium phosphate 0.4 1 (# 12) 30 3 120 6.1 15 tin phosphate 0.5 1 (# 13) 30 3 120 6.1 16 Zirconium Phosphate 2.0 4 60 3 108 5.7 17 Zirconium Phosphate 0.5 5 60 3 110 5.5 18 titanium phosphate 0.5 6 60 3 110 5.5 19 hafnium phosphate 0.5 7 60 3 110 5.5 20 tin phosphate 0.5 8 60 3 110 5.5 Table III (Continuation) Results space-time no. Conversion Product By-product Yield (%) Class Selective Class selectivity class selectivity products (wt .-%) (wt .-%) (wt .-%) (g / l h) 1 15.3 MIBK 96.2 IPA 0.6 DIBK 3.0 -2 15.6 MIBK 95.8 IPA 1.0 DIBK 3.1 410 3 18.7 MIBK 74.8 IPA 24.0 - - -4 23.6 MIBK 65.2 IPA 28.0 - - -5 14.0 MIBK 95.5 - - - - -6 13.4 MIBK 95.0 - - - - -7 15.0 MIBK 96.4 - - - - -8 14.6 MIBK 95.5 - - - - -9 16.1 MIBK 89.1 IPA 2.6 DIBK 7.8 -10 17.8 MIBK 92.3 IPA 5.1 DIBK 2.3 -11 17.0 MIBK 91.1 IPA 6.5 DIBK 2.0 -12 12.0 MIBK 92.7 - - - - -13 18.0 MIBK 91.0 IPA 1.6 DIBK 5.6 -14 14.0 MIBK 94.3 - - - - -15 6.5 MIBK 93.0 - - - - -16 10.6 MIBK 91.0 IPA 3.4 DIBK 5.3 -17 12.6 MIBK 95.7 - - - - -18 11.4 MIBK 93.5 - - - - -19 10.0 MIBK 94.0 - - - - -20 5.3 MIBK 93.0 - - - - - Example 10 Dimerization and Saturation reaction of acetone Min was made from acetone using 15 ml of zirconium phosphate catalyst with a palladium content of 0.5% by weight, the naoh no. 1 dc. Example 1 obtained using the same apparatus as in Example 9 and modification the reaction temperature and pressure as well as the charge amounts Acetone and hydrogen as indicated in Table IV. The received Results are given in Table IV.

Table IV No. Temperature Pressure Acetone H2 Conversion Selectivity (%) Space-time- (° C) (kg / cm²) (ml / h) (l / h) treatment MIBK IPA DIBK yield (%) of MIBK (g / l h) 1 120 5.5 60 3 23.1 91 1.9 6.1 570 2 112 5.5 60 3 16.3 93 1.2 5.4 410 3 102 5.5 60 3 14.3 97 0.5 2.5 380 4 114 5.6 60 4 18.3 91.0 1.2 5.9 470 5 114 5.6 75 5 15.3 93.4 0.8 6.5 480 6 114 5.6 105 7 12.7 96.1 0.5 5.8 580 7 102 8.8 60 5 14.8 92.1 5.7 2.2 370 8 102 7.6 60 5 15.1 94.3 4.0 1.7 390 9 102 5.7 60 5 14.7 94.7 2.8 2.4 380 10 102 2.8 60 5 16.0 92.3 1.6 6.1 400 11 120 6.7 60 3 18.1 94.6 0.6 4.1 470 12 120 6.7 60 6 19.2 92.6 1.0 4.9 480 13 120 6.7 60 8 22.4 86.2 5.5 6.8 480 14 120 6.7 60 10 25.2 82.1 9.3 8.0 560 Example 11 Dimerization and Saturation reaction of different ketones 15 ml each of the tests 1, 11, 12 and 11 of the example 1 obtained catalysts were in the middle part of a corresponding packed into the reaction tube used in Example 9, and the reactions were carried out carried out between the different classes of ketones and hydrogen, being the results shown in Table V were obtained. Those used in Table V. Abbreviations represent the following compounds: MEK = methyl ethyl ketone DEK = Diethyl ketone MIBK = methyl isobutyl ketone DNK = dinonyl ketone MCK = methyl cyclohexyl ketone APR r acetophenone MHO = 3-methylheptan-5-one EMHO = 3-ethyl-4-methylheptan-5-one TMNO = 2,6,8-trimethylnonan-4-one ONHO = 11-octyl-12-nonylheneicosan-10-one DCHB = 2,4-dicyclohexylbutan-4-one PPPK = S-phenyl-propyl phenyl ketone Table V No. Ketones used Catalyst Reaction Conditions Results Class Example Tempe- Pressure Hourly H2 / ketone Um- product no. Rature (kg / cm²) liquid k @ it @ - (molar wall- (° C) room g @@@@ win- ratio (%) characte- rity (LSHV) (h-1) ratio (mol%) 1 MEK Zirconium phosphate 1 145 6.8 2.0 0.2 10.2 MHO 94.2 2 MEK titanium phosphate 10 145 6.8 2.0 0.2 10.0 MHO 95.0 3 MEK Hafnium Phosphate 11 145 6.8 2.0 0.2 7.7 MHO 94.0 4 MEK Tin phosphate 12 145 6.8 2.0 0.2 3.5 MHO 94.4 5 DEK zirconium phosphate 1 105 2.0 4.0 0.2 6.3 EMHO 96.5 6 DEK titanium phosphate 10 105 2.0 4.0 0.2 5.5 EMHO 96.0 7 MIBK zirconium phosphate 1 202 1.0 0.425 1.1 42.0 TMNO 82.2 8 MIBK titanium phosphate 10 202 1.0 0.425 1.1 38.5 TMNO 84.0 9 DNK zirconium phosphate 1 130 1.0 2.0 0.4 6.3 ONHO 85.3 10 DNK titanium phosphate 10 130 1.0 2.0 0.4 5.9 ONHO 83.5 11 DNK hafnium phosphate 11 130 1.0 2.0 0.4 4.0 ONHO 86.0 12 DNK tin phosphate 12 130 1.0 2.0 0.4 1.8 ONHO 82.1 13 MCK zirconium phosphate 1 130 1.0 2.0 0.2 6.5 DCHB 82.0 14 MCK titanium phosphate 10 130 1.0 2.0 0.2 6.0 DCHB 80.0 15 APH zirconium phosphate 1 200 1.0 1.0 0.2 4.7 PPPK 79.2 16 APH titanium phosphate 10 200 1.0 1.0 0.2 4.3 PPPK 77.4 17 APH hafnium phosphate 11 200 1.0 1.0 0.2 3.8 PPPK 78.0 18 APH tin phosphate 12 200 1.0 1.0 0.2 1.5 PPPL 71.2 example 12 Dimerization and saturation reactions of different ketones 15 ml each of the different ketones Catalysts obtained in Examples 5 to 8 were used and the reactions between the different classes of ketones and hydrogen were carried out by placing these catalysts in the middle part of a reaction tube according to the used in Example 9, with the results reported in Table VI are. The abbreviations used in this table are the same as those in Example 11.

Table VI No. Keto- Catalyst used Reaction conditions Results ne class example tempe- pressure hourly H2 / ketone Um- product no. Temperature (kg / che fluid (molar ratio (° C) cm²) fluid ratio) (%) drawing speed (h-1) (mol%) 1 MEK zirconium phosphate 5 145 6.8 2.0 0.2 9.1 MHO 94.0 2 MEK titanium phosphate 6 145 6.8 2.0 0.2 8.5 MHO 94.5 3 MEK Hafnium phosphate 7 145 6.8 2.0 0.2 7.0 MHO 94.0 4 MEK tin phosphate 8 145 6.8 2.0 0.2 3.0 MHO 93.0 5 DEK zirconium phosphate 5 105 2.0 4.0 0.2 6.0 EMHO 96.0 6 DEK titanium phosphate 6 105 2.0 4.0 0.2 5.2 EMHO 96.0 7 MIBK zirconium phosphate 5 200 1.0 0.425 1.1 35.6 TMNO 81.1 8 MIBK titanium phosphate 6 200 1.0 0.425 1.1 31.4 TMNO 85.4 9 DNK zirconium phosphate 5 130 1.0 2.0 0.4 5.0 ONHO 84.0 10 DNK titanium phosphate 6 130 1.0 2.0 0.4 5.0 ONHO 83.0 11 DNK hafnium phosphate 7 130 1.0 2.0 0.4 3.7 ONHO 83.0 12 DNK tin phosphate 8 130 1.0 2.0 0.4 1.4 ONHO 81.0 13 MCK zirconium phosphate 5 130 1.0 2.0 0.2 5.3 DCHB 82.0 14 MCK titanium phosphate 6 130 1.0 2.0 0.2 5.0 DCHB 80.0 15 APH zirconium phosphate 5 200 1.0 1.0 0.2 4.0 PPPK 78.0 16 APH titanium phosphate 6 200 1.0 1.0 0.2 4.0 PPPK 75.0 17 APH hafnium phosphate 7 200 1.0 1.0 0.2 3.5 PPPK 76.0 18 APH tin phosphate 8 200 1.0 1.0 0.2 1.0 PPPK 73.0 Example 13 Dimerization and Saturation Reaction 4 ml of acetone and methyl ethyl ketone obtained in Experiment 1 of Example 1 Catalyst were in the middle part of a Pyrex reaction tube @ 40 cm in length and 12 mm in diameter, and then a mixture of acetone and Methyl ethyl ketone in a molar ratio of 1: 1 and hydrogen lit velocities of 1.7 @@ / h or 5.8 ml / h under the conditions of a reaction temperature of 175 ° C introduced.

This resulted in the following composition of the reaction product: Acetone 20.4 mol%, methyl ethyl ketone 29.9 mol%, methyl isobutyl ketone 10.2 mol%, 2-methylhexan-4-one 9.7 mol%, 3-methylhexan-5-one 5.0 mol%, 3-methylheptan-5-one 3.1 mol%, diisobutyl ketone 9.4 mol%, 2-methyl-4-ethylheptan-6-one 6.6 mol%, 2,6,8-trimethylnonanone 2.2 mol% and reat 3.5%.

Example 14 Dimerization and saturation reaction of acetone and Diphenyl ketone In an externally heated 300 ml autoclave, 100 g of one Diphenyl ketone / acetone mixtures (molar ratio 9: 1) and 10 g of that in Experiment 1 of the example 1 obtained zirconium phosphate catalyst with 0.5 wt .-% palladium introduced. After introducing hydrogen to a pressure of 5.0 kg / cm² at room temperature was the reaction for 2 hours at 150 ° C at a maximum pressure of 21 kg / cm². The product had the following composition in mol%: unreacted Diphenyl ketone 93%, unreacted acetone 2%, methyl isobutyl ketone 3% and 1,1-diphenylbutan-3-one 2%.

Example 15 Dimerization and Saturation Reaction of Acetone 15 g the zirconium phosphate produced according to the process described in Example 4, Paragraph 1, which had been crushed to 2.4 to 1.7 mm (8 - 12 nesh) were dissolved in 50 ml of 1N HCl, in which 0.17 g of palladium chloride was dissolved, immersed. The zirconium phosphate was left stand in this state for 24 hours, and then it was under reduced Pressure dried at 100 ° C, then for 8 hours in a stream of hydrogen 400 ° C subjected to a reducing treatment, and a zirconium phosphate catalyst was obtained, d @@@ en palladium content was 0.7% by weight. 15 ml of this catalyst were in a The reaction was packed and the reaction was continued while introducing acetone and hydrogen at a rate of 60 ml / h or 4 l / h under temperature conditions of 120 ° C and a pressure of 6.2 kg / cm². There was a transformation of 16.0% and the following yields, based on weight, were obtained: MIBK 88.6 %, IPA 5.3%, DIBK 2.0% and mesityl oxide 3.2%.

Example 16 Dimerization and Saturation Reaction of Acetone 8 g commercial palladium (containing 2.5% by weight palladium in activated carbon) to 30 g of the zirconium phosphate prepared as described in paragraph (1) of Example 4 was obtained, added and during 15 hours in one Kneader mixed. Thereafter, the mixture became pellets with a diameter of 5 mm and pressed to a height of 3 n.

The pellets were cut to a particle size of 2.4 to 1.7 mm (8 -12 mesh J JIS) and then for 8 hours at a temperature of 400 ° C subjected to a hydrogen treatment. 15 ml of the catalyst thus obtained were packed in a reaction tube and the reaction was carried out as in Example 15, taking acetone and hydrogen at rates of 60 ml / h and 4 l / h respectively Temperature and pressure conditions of 120 ° C and 6.2 kg / cm² were introduced. the Conversion of the concrete was 15.8% and the yield was as follows: MIBK 85.8% by weight, IPA 7.0% by weight, DIBK 1.8% by weight and mesityl oxide 4.7% by weight.

Example 17 Dimerization and Saturation Reaction of Acetone After Addition of 0.) g of commercially available black palladium powder to 30 g of zirconium phosphate, obtained as described in paragraph (1) of Example 4 and mixing the two components with a kneader for about 15 hours became the mixture compression-molded into pellets with a diameter of 5 mm and a height of 3 mm. The pellets were crushed to a particle size of 2.4 to 1.7 (8-12 mesh JIS) and then a hydrogen treatment for 8 hours at a temperature of 400 ° C subject. 15 ml of the mixed catalyst thus obtained was placed in a reaction tube packed, and acetone and hydrogen were added under identical conditions as in Example 15 implemented, with a conversion of acetone of 13.4% and the following yields of MIBK, IPA, DIBK and mesityl oxide (@O) were obtained: 81.7% by weight, 7.5% by weight, 2.0 wt% and 8.0 wt%, respectively.

Example 18 Dimerization and Saturation Reaction of Acetone 8 s Commercial palladium catalyst (containing 2.5% by weight of palladium in activated carbon) was added to 30 g of the zirconium phosphate obtained in Example 6, and the the two components were mixed in a kneader for about 15 hours. That The mixture then became pellets with a diameter of 5 mm and a height of 3 mm pressed. The pellets were cut to a size of 2.4 to 1.7 mm (8-12 mesh JIS) and subjected to hydrogen treatment for 8 hours at a temperature of 400 ° C subject. 15 ml of the mixed clay catalyst thus obtained was placed in a reaction tube packed, and di.

Reaction between acetone and hydrogen was carried out under identical conditions, as indicated in Example 15, with a conversion of acetone of 13.5% and the following yields in MIKB, IPA, DIBK and mesityl oxide gave: 86.0 Wt%, 6.3 wt%, 2.0 wt% and 5.7 wt%.

Example 19 Dimerization and Saturation Reaction of Various Ketones 15 ml each of the catalysts obtained in Beispiolo @ @@ and 18 were in the same reaction tube as used in Example 9, packed, and the reactions of the various classes of ketones and hydrogen were carried out, whereby did not set the results shown in Table VII. The in Table VII Abbreviations used were identical to those used in Example 11.

Table VII Catalyst Used Reaction Conditions Results No. Ketone class Ex. Tem- Pressure hour- H2 / Ketone Um- Product No. pera- (kg / cm²) liche (Molver- con - selecture fluid) drawing drawing (° C) iqui- ty @ - (%) speed space- (mol-%) speed (h-1) 1 MEK zirconium phosphate 14 145 7.0 2.0 0.2 8 MHO 85 2 MEK titanium phosphate 16 145 7.0 2.0 0.2 7 MHO 85 3 DEK zirconium phosphate 14 105 2.0 4.0 0.2 5 EMHO 83 4 DEK titanium phosphate 16 105 2.0 4.0 0.2 4 EMHO 85 5 MIBK zirconium phosphate 14 200 1.0 0.4 1.0 29 TMNO 70 6 D @ K zirconium phosphate 14 130 1.0 2.0 0.4 4 ONHO 71 7 MCK zirconium phosphate 14 130 1.0 2.0 0.2 3 DCHB 73

Claims (14)

Claims 1. Process on production of dimerized saturated Ketones, characterized in that ketones consisting of (a) at least one Ketone with at least one on either one or both of the carbon atoms with linked to the carbonyl group, bonded water vapor or (b) a ketone with at least two on either one or both of the carbon atoms associated with the Carbonyl group, bonded hydrogen atoms and a ketone that is no has hydrogen atom bonded to these carbon atoms, to a temperature from 60 to 400 ° C together with hydrogen in the presence of a metallic palladium and a phosphate at least one of the metals zirconium, titanium, hafnium or tin containing catalyst heated. 2. The method according to claim 1, characterized in that the Ketones are heated to a temperature in the range of 80 to 250 ° C, whereby the ketones from the same or different classes of the ketones defined in (a) or consisting of two classes of the ketones defined in (b), 3. The method according to claim 1 or 2, characterized in that the pressure within the reaction aeyotone to 1 to 50 kg / cm², preferably 1 to 30 kg / cm². 4. The method according to claim 1 bi @ 3, characterized in that the Ketones in the liquid P @@@@ ung @@@ tzt. 5. @@@@@@@@@ @@@ @@@@@@ @ to 4, thereby identified hydrogen be converted to ketones in the range from 0.1 to 1.0. 6. The method according to claim 1 to 5, characterized in that at least one of the ketones acetone, methyl ethyl ketone, methyl isobutyl ketone or diethyl ketone is dimerized. 7. The method according to claim 1 to 6, characterized in e i c h n e t, that a catalyst is used, the metallic palladium and a phosphate contains at least one of the metals zirconium, titanium, hafnium or tin, whereby the catalyst 0.1 to 5.3% by weight, based on the metal phosphate, of metallic Contains palladium, 8. The method according to claim 1 to 7, characterized in -z e i c h n e t that a catalyst is used which is a phosphate of at least one of the Metals containing zirconium, titanium, hafnium or tin, on which metallic palladium is upset. 9. The method according to claim 1 to 8, characterized in that one a catalyst is used, which by reducing treatment of a lower precipitate, the reaction of a water-soluble salt at least one of the metals zirconium, Titanium, hafnium or tin with phosphate ions (PO4-3) in the presence of a water-soluble one Palladium salses in a pH range of 3.0 to 12.0 was prepared became. 10. The method according to claim 1 to 8, characterized in e i c h n e t that one uses a catalyst which is produced by converting a water-soluble Salt little @ ten @ one of the metals zirconium, titanium, hafnium or zinc with phosphate ions (PO4-3) in a molar ratio PO4-3 / Me of the phosphate ions to metal @ al @ of 1: 0.6 up to 1.7 with the production of a metal phosphate, then bring into @ erience of Metal phosphates with an aqueous solution of a water-soluble palladium salt in a pH range from 3.0 to 10.0 and subsequent reducing treatment of the metal phosphate was obtained. 11. The method according to claim 1 to 8, characterized in that it e n n z e i c h n e t that a catalyst is used, which by adjusting a water-soluble Salt of at least one of the metals zirconium, titanium, hafnium or tin and phosphate ions to a pH of 3 to 12 and reacting the ingredients to form a Metal phosphate, then bringing the metal phosphate together with an aqueous one Solution of a water-soluble palladium salt in a pH range from 3.0 to 10.0 and subsequent reducing treatment of the metal phosphate was obtained. 12. The method according to claim 11, characterized in that i c h n e t a metal phosphate is used, which is obtained by adjusting the water-soluble salt at least one of the metals zirconium, titanium, hafnium or tin and the phosphate ions to a pH range of 3 to 12 using ammoni @ k or a caustic alkali was obtained, and that the reaction is then carried out. 13. The method according to claim 9 bie 11, characterized in that there are no e n n z e i c h n e t that the reducing treatment is carried out by heating in a stream of hydrogen is carried out to 100 to 600 ° C. 14. The method according to claim 1 to 6, characterized in that the catalyst used is a mixture of metallic palladium and one by reaction of a water soluble salt at least one of the metals zirconium, titanium, hafnium or metal phosphate obtained with tin with phosphate ions is used.