DE1922755C3 - Process for the preparation of dimerized saturated ketones - Google Patents

Description

15th

The invention relates to a method for producing jo dimerized. saturated ketones by dimerizing a ketone from the group consisting of
A at least one ketone which contains at least one hydrogen atom in the x or in the x and α positions to the carbonyl group, or} i B. the mixture of a) a ketone with at least two carbon atoms either on one or both of the carbonyl group bonded hydrogen atoms and b) a ketone which does not contain a hydrogen atom on the carbon atoms bonded to the carbonyl group, in the presence of hydrogen on metallic palladium-containing catalysts at elevated temperature, which is characterized. that the reaction at a temperature of 80 to 250 ° C and a pressure of 1 to -r, 50 kg / cm ^? carried out in the presence of a catalyst, the active ingredient a ') a phosphate of at least one of the metals zirconium, titanium and hafnium and b') 0.1 to 5J wt .-% metallic palladium, based on the metal phosphate deposited in this phosphate is, contains.

In the production of saturated ketones by dicnerizing condensation of ketones and subsequent Hydrogenation of the same has been customary up to now, first of all the condensation reaction of the ketones under> ϊ To carry out application of an alkali, then the resulting ketol with subsequent dehydration to convert to unsaturated ketones and finally these unsaturated ketones to a hydrogenation stage subject. In this method, in addition to the fact that the work steps were complicated, also occurred the disadvantages that the yield due to the relative low conversion during the condensation stage fe was low and that significant amounts of the carbinol by-product during the hydrogenation step were formed.

Furthermore, a method is known in which the Dimefize unsaturated ketones by direct from two molecules of the ketones were formed using a molecular sieve as a catalyst and then the unsaturated ketones obtained were subjected to the hydrogenation stage. This method has the disadvantages that not only is the catalyst activity of the molecular sieves insufficient, but that also the decrease in the activity of the catalysts with the lapse of time is great. It is still there necessary the hydrogenation reaction as a separate stage perform.

The aim of the invention is to eliminate the disadvantages of the known methods.

The metal phosphates

The metal phosphates to be used in the context of the invention are obtained by reacting phosphoric acid with one or more water-soluble salts of zirconium, titanium or hafnium and isolating the precipitate obtained. Since the above reaction is a reaction between the above metals (Me) and phosphate ions (PO4 ^J ) in an aqueous medium, the phosphoric acid need not necessarily consist of phosphoric acid itself, but can be any compound which provides the phosphate ions in an aqueous medium . Examples include the neutral and acidic salts of phosphoric acid, including those of sodium. Potassium, lithium and ammonium and the acidic salts of phosphoric acid including those of magnesium and calcium and other water-soluble phosphates. Of these, phosphoric acid and the acidic salts of phosphoric acid are preferred, but in particular phosphoric acid.

On the other hand, as water-soluble salts of zircon. Titans and Hafniums all used that will provide these metal ions, however the halides are particularly preferred. Oxyhalides, oxynitrates and oxysulfates of these metals.

All known processes for the implementation of one or more of the water-soluble salts of zirconium, Titanium or hafnium with the phosphate ions in an aqueous medium for the production of zirconium, titanium or Hafnium phosphate can be used. For example, all methods according to |. Inorg. and Nucl. Chem., Vol. 6. pp. 220-235 (1958). and Vol. 26, pp. 117 to 129 (1964). and Vol. 28 pp. 607 to 613 (1% 6) can be applied.

Since the molar ratio POi '/ Me is not particularly limited and each component can be used in a large amount, a range in which one of the components does not exceed three times the molar amount of the other is generally favorable from the viewpoint of economy . According to a preferred embodiment, the molar ratio PO »VMe is 0.6 to 1.7. Particularly good results are obtained here, since metaphosphates with a large specific surface area are obtained before. In this case it is particularly favorable that the precipitation of the metal phosphates takes place from a solution with a low concentration. Particularly favorable results are obtained when three precipitates are dried without heating,

Furthermore, the metaphosphates, which were obtained by drying the gelatinous precipitates, have those, in turn, by reacting the water-soluble salts of the above metals with the phosphate ions in an aqueous solution with a pH of less than 3 or more and preferably pH 12 or less formed

also have a particularly large specific surface and can therefore be used advantageously will.

In this case it is possible to have each of the components in a substantial excess over the other use. To adjust the pH of the reaction system to 3 to 12 in this case, the the following procedures are preferred:

(1) Adding a strong alkali to the reaction sy- stem star, for example caustic alkalis, caustic alkalis and alkali carbonates and

(2) Adding ammonia to the reaction system.

In the case (1), however, there is a tendency that a part π of the metal phosphates obtained is substituted by alkali metals or alkaline earth metals Method (2) is applied is a part of the obtained metal phosphates by ammonium ions substituted. Therefore the metal phosphates are preferred in their acid form (H-Furrn or H-Typ) by replacing the aforementioned alkali ions, alkaline earth ions or ammonium ions with hydrogen converted.

In the case of process (1) this is done in that r> the precipitate obtained after completion of the reaction is treated with an acid, whereby the hydrogen atoms displace the partially substituting alkali or alkaline earth metal ions, while in the case of process (2) that after completion jn the reaction erh.'liene precipitate is dried by heating is up to 600 ⁰ C. whereby the ammonia is removed, for example, on the 300th

Metallic Pallad m

yy

For this purpose, all water-soluble palladium compounds, for example palladium sulfate, Palladium nitrate and palladium halides can be used.

Manufacture of the catalyst

The catalysts which can be used in the context of the invention can be prepared in any way provided that they are metallic palladium and the aforesaid metal phosphates in one state in which the metallic palladium is supported on the phosphate. These catalysts can jo can be used as is, or after being kept on inert carriers such as diatomaceous earth. Aluminum oxide, silica. Activated charcoal or clay. -, η be applied. Furthermore, the catalysts of the invention can either be in powder form or Granulate form can be used.

It is preferable to use (1) a method in which a water-soluble palladium salt is added and dissolved in the system y during the reaction for preparing the above metal phosphates, whereupon the moisture content is evaporated and then the palladium salt supported on the phosphate is subjected to a reduction treatment. (2) a method in which the preformed metal phosphates are immersed in an aqueous solution of a water-soluble palladium salt, then the moisture content is evaporated and then the palladium salt supported on the phosphate is subjected to a reduction treatment, and (3) a method in which palladium ions in the Katiönische Lönenäusiauschgruppe of the metal

40

4-, phosphdte are introduced and then the reduction treatment is carried out.

When the catalysts according to the above-described methods (1), (2) and (3) and in particular were obtained by the method (3), excellent catalysts are obtained in which the metallic palladium is deposited uniformly and in a very finely divided state

The process for introducing the palladium ions by ion exchange into the cationic exchange group of the metal phosphates is usually carried out by adjusting the pH of the solution which contains the water-soluble palladium salt in the preparation of the catalyst. When introducing palladium as ions into the cationic exchange groups of the metal phosphates, it is preferred to use substances which, by reaction with the palladium salt, form stable cationic ions of palladium in aqueous solution. As such substances, there are usually ammonium hydroxide and water-soluble organic amines such as methylamine and alhyiamine. cheap. These compounds have the advantage that they react with the palladium salts and convert the palladium into stable, water-soluble complex cations and at the same time regulate the pH of the reaction solution so that the ion exchange of the palladium ^{ca 1} ions with the Kat.onen of the metal phosphate is easy will. This method is common especially in the case where the palladium salt is introduced in the form of palladium tetrammine complex ions [Pd (NHj) ₄ ] ² * and the ion exchange of the complex ions with the cationic exchange group of the above metal phosphates is carried out using ammonium hydroxide the most effective.

If the pH of the solution is S to 12 and preferably 4 to 7 when carrying out the ion exchange between palladium ions and the cationic exchange group dv .. · metal phosphates is retained, the ion exchange of the palladium ions is preferably carried out independently of the Concentration of the palladium ions. On the other hand, if the pH of the solution is less than 3; H. a State where the hydrogen ion concentration is large. the ion exchange of hydrogen proceeds ions proceed to the cationic exchange group of the metal phosphates, with either the introduction the palladium ions is inhibited or the palladium in Remains impregnated in the form of a palladium salt. Compared to a catalytic converter that protrudes in one The indicated pH range is a Catalyst made with a solution with a pH below 3, with regard to its Selectivity for the intended dimerized saturated ketones somewhat poorer. If the pH is the The above palladium-containing solution is greater than 12. the palladium is not completely ionized introduced what entails. that the selectivity for dimensized saturated ketones of the catalyst obtained in this case also gets a little worse.

As a process for introducing the palladium ions into the Kalionenäüstaticgrtlppe of the zircon *, titanium * Or hafnium phosphate is usually beneficial either the simultaneous ion exchange method which the palladium unications by ion exchange during the time of the production of the above metal phos * phate are introduced, or the sequential ion exchange method used, in which the palla

diumkationen are introduced into the cation exchange group of the metal phosphates after this Metal phosphates were obtained. The catalyst obtained by the simultaneous ion exchange method is particularly effective.

The simultaneous: ion exchange method is carried out in the following way: z. B. will initially be a Palladium salt in an aqueous one or more water-soluble salts of zirconium, titanium, hafnium and Solution containing tin dissolved. Then this aqueous solution is either with phosphoric acid or a water-soluble phosphate with the simultaneous presence of a for the formation of stable palladium cations in the aqueous solution by reaction with the palladium salt capable substance (hereinafter referred to as a Palladium cation forming agent called), e.g. B. ammonium hydroxide, reacted while the pH of the reaction solution is kept in the range of 3 to 12 and in this way a hydrogel of the metal phosphate produced by ion exchange with palladium cations. and then that Hydrogel filtered off. The above-mentioned palladium cations Forming agents may be added to the phosphoric acid or the aqueous phosphate solution in advance or it can be added to the solution after the above-mentioned hydrogel is formed.

On the other hand, the sequential ion exchange method is carried out in the following way:

Pre-prepared zirconium, titanium or hafnium phosphate is immersed in a solution containing stable palladium cations, e.g. B- [PdA ₄ ] * *. where A is NH). CHiNH: or CjHsNHj means, and the ion exchange takes place in a standstill state, or the above metal phosphate is packed in a column through which a solution containing the palladium cations is passed, the ion exchange taking place in an optimal manner. The metal phosphate containing the exchanged ions is then thoroughly washed with water. In this way the metal phosphate is obtained by effecting the ion exchange with palladium cations.

The phosphates of at least one of the metals zirconium. Titanium or hafnium, as described above or obtained by other known methods and into which palladium cations by ion exchange methods have been introduced, are then subjected to a reducing treatment to remove the palladium cations to be converted into metallic palladium. The metal phosphates can therefore be converted into their acid form be transferred, and at the same time, metallic palladium can be uniformly applied to the metal phosphates and applied in a very finely divided state. According to the ion exchange method described above the palladium on the metal phosphates given above is very finely divided metallic palladium with a particle diameter of not more than 100 A is applied.

To the above according to the invention to be applied to reduction treatment, for example, the calcination of the metal phosphates are obtained after ion-exchange in a stream of hydrogen at 100 to 600 ° C and preferably 300 to 500 ⁰ C; the process in which it is first ^{calcined in air at 200 to 500 °} C. and then the reduction is carried out in a reducing atmosphere, for example a stream of hydrogen, and the process in which the reduction treatment is carried out using known reducing agents such as formaldehyde, formic acid , Sodium borohydride and hydrazine, and then subjecting the metal phosphate to an acid treatment to remove the ammonium ion in the cases where the above reducing agents have been used.

The amount of metallic palladium contained in the catalyst according to the invention is between 0.1 and 5.3 percent by weight and especially between

! U 0.2 and 3.0 percent by weight, based on the Metal phosphate. When the content of metallic palladium is below the above range the by-products take predominantly the trimeric condensation products of the starting ketone when the palladium content exceeds the above range, the formation of carbinol easily increases.

The site of activity necessary for the dimerization condensation reaction (hereinafter referred to as simple condensation) of ketones is effective. is the

: <> Acid ion exchange group of the metal phosphates select rend as a site of activity that ici · the hydrogenation of the dimensioned ketones produced by condensation is effective. the metallic palladium is accepted.

Reaction conditions

The reaction temperature is 80 to 250 ° C. the pressure 1 to 50 kg / cm- 'and preferably 1 to 30 kg / cm-'. The molar ratio of hydrogen to ketones is

jo preferably at 0.01 to 2.0. especially at 0.1 to 1.0. The reaction can take place in the liquid or vapor phase. However, there is a tendency to increase the Formation of various by-products, of which the trimerized condensation product predominates,

Ji stands when the ketones are implemented in the vapor phase working in the liquid phase is preferred. In this case, the results are generally good achieved when the liquid hourly space velocity of the ketones is in a range from 1 to 20 (Liquid volume / catalyst volume / hour) held will.

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 of hydrogen to the Au <= gang ketones and particularly influenced by the latter. Appropriate conditions should therefore depend on can be chosen from the output ketones. The influence of the reaction pressure on the formation of by-products however, it is small compared to the influence of the hydrogen-Kf ton molar ratio.

The response can be batch or continuous be performed. In the continuous method, the known reaction methods and apparatuses can be used used with a fixed catalyst bed, fluidized bed catalyst or fluidized bed will.

Ketones

Ketones falling under (A) of the above definition include ketones represented by the following formula

R ₁ COCH

Sn where Ri is an alkyl, cycloalkyl, aryl, aralkyl,

Alkaryl or alkenyl radical and R ₂ and Rj, which can be the same or different, each denote hydrogen, an alkyl, cycloalkyl, aryl, aralkyl, alkaryl or alkenyl radical, and those ketones in which the total sum of the carbon atoms 3 to 19 are appropriately used.

To ketones which fall under the above definition B, b include, for example, diphenyl ketone and di-tert-butyl ketone.

The reaction is preferably carried out between ketones of a single class, as there are a plurality of P: Product classes are formed when the reaction is carried out with a ketone mixture of different classes as a result, the separation becomes complicated.

For specific examples of this in accordance with the fertilization requirements Process usable ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, Methyl isobutyl ketone, ethyl hexyl ketone, dinonyl kelon, acetophenone, ivietnyicycionexyikeion, isopfopyi-ieri.-butyl ketone and isopropyl phenyl ketone.

The production of the catalysts used according to the invention is described below, which is not claimed.

Those given under No. 1 to 12 of Table I. various water-soluble metal salts were dissolved in water and then the various under No. 1 to 12 of the table specified water-soluble

Some palladium salts are dissolved by heating. The one in the Phosphorsäurekoniponenteh listed in the table separately dissolved in water. At first, the first-mentioned solution slowly became the last said solution is added at room temperature with stirring, after which ammonia water (concentrated Ammonia water, unless otherwise stated) was added until the pH value given in Table I. was achieved. The solution was then stirred for 4 hours and then left to stand still for 24 hours.

The resulting precipitate was filtered, washed with water and dried after removal of the remaining unreacted portion of the above salts at 110 ⁰ G, the gel-like metal phosphates listed in Table I were obtained

Hi fjfif ucii ΐίίίί Pänauiiiffikaiiuficfi Substitutes tv'urcii. The so gel-like products obtained were pulverized to a grain size of 2.4 to 1.7 mm, after which they were in were calcined in a stream of hydrogen at 400 ° C. for 8 hours.

Tabel Used metal salt Trains water Phosphoric acid constituents , · 2H ₂ O Trains pH of the water Palladium salt Trains : I. Great given to the Great given Reaction solution to the Great given
lot Catalyst components lot Dissolve lot Dissolve (G) Kata (G) (I) (G) (I) 0.71 lyser
No. 97 6th 70 5.0 6th 0.50 ZrOCl ₂ · 8H ₂ O 97 6th H ₁ PO ₄ 35 4.8 6th PdCl ₂ 0.71 the same 97 2 H ₃ PO ₄ 70 7.6 2 PdCI ₂ 1.4 the same 97 2 H ₃ PO ₄ 70 4.0 2 PdCl ₂ OjO 1 the same 97 6th HjPO ₄ 56 5.0 6th PdCI ₂ ) ₂ 052 2 the same 97 6th NaH ₂ PO. 70 5.0 6th PdCI ₂ 2H ₂ O 0.96 3 the same 97 6th HjPO ₄ 70 5.0 6th Pd (NO ₃ ; 0.28 4th the same 97 6th H ₃ PO ₄ 70 5.0 6th PdSO ₄ - 1.42 5 the same 97 6th H ₃ PO ₄ 70 6th PdCI ₂ 2.15 6th the same 97 6th H ₃ PO ₄ 70 6th PdCI ₂ 0.80 7th the same 57 5 HjPO ₄ 70 5 PdCI ₂ 03 8th TiCl ₄ 41 3 H ₃ PO ₄ 24 3 PdCI ₂ 9 HfOCl ₂ · 8H ₂ O H ₃ PO ₄ PdCI ₂ 10 (Continuation) Catalyst preparation conditions 11th Kataly Obtained catalyst Pd content 12th sator No. Connection to the setting Mole ratio Great (Weight development of the pH value percent) Oj (ml) Oj 1 NH ₄ OH 72 Oj 2 NHiOH 60 (PO ₄ VMe) Oj 3 NHiOH 90 Room Oj 4th NHiOH 90 1.0 Oj 5 1 n-NHi0H ZO Oj 6th NHiOH ZO Zirconium phosphate 02 7th NHOH 1.0 desgL 8th NHiOH ZO ZO Zirconium phosphate ZO desgL desgL desgL ~~ ---Tr-
desd.

9 19th 2.0
2.0
2.0
2.0 22 755 IO I'd salary
(Weight
per / cm) Fortsel / iiiig 1.0
1.5
0.8
0.4 Catalysis
sa lor
No. Catalyzerslkmgsbedtiigiingeii
Connection to the Einsiel molar ratio
lung of the pll-Weries
(ml) (PO ₄ VMe) pH Wen der
Reaction solution F.rhallener Kulalysalor
Great IO
Π
12th NH ₄ OH
NH ₄ OH
NH ₄ OH
I n -NH ₄ OH 5.0
5.0
5.0
5.0 the same
the same
Titanium phosphate
Hafnium phosphate

During the experiments to produce the catalysts

1 and 3 in Table I was used to adjust the pH value of ammonia water in amounts of 7.2 and

2 to adjust the pH value 60 ml ammonia water immediately after diluting the phosphoric acid with Water is added and then, for the preparation of the catalyst, with an aqueous zirconium oxychloride solution mixed.

Catalytic converter 13

After dissolving 97 g of zirconium oxychloride (ZrOCI ₂ · 8 H ₂ O) in 61 water, 0.71 g of palladium chloride was dissolved therein with heating. On the other hand, 70 g of phosphoric acid were diluted with 6 l of water. The former solution was then added to the latter with stirring at room temperature, after which the pH of the reaction solution was adjusted by adding 40% aqueous methylamine solution with continuous stirring. The PO ₄ -VZr molar ratio at this point in time was 2.0. Stirring was then continued for a further 4 hours, after which the reaction solution was allowed to stand for 24 hours. The resulting precipitate was then filtered off, washed with water and ^{dried at HO °} C. Thereafter, the precipitate was pulverized to a particle size of 2.4 to 1.7 mm (8 to 12 mesh JIS) and at 300 ^° C. for 3 hours in air Subsequently, the calcined product calcined for 6 hours at 400 ⁰ C in a stream of hydrogen was subjected to a reducing treatment, and to give a Zirkonphosphatkatalysator whose palladium content was 0.5 weight percent.

Catalyst 14

Dried gel, which had been obtained under identical conditions as for the preparation of catalyst 2, was pulverized to a particle size of 2.4 to 1.7 mm and then subjected to a reducing treatment using formaldehyde vapor ^{at 100 ° C. for 4 hours.} The gel was then impregnated with 0.1 N HCl for 24 hours at room temperature to remove the ammonium ions, then washed with water until free from chlorine ions and then dried at 110 ° C., a zirconium phosphate catalyst with a palladium content of 0.5 percent by weight being obtained .

Catalytic converter 15

1. 35 g of phosphoric acid was diluted with 31% of water. On the other hand, there was 97 g of zirconium oxychloride The two solutions were then dissolved in 31 water Reacted by moving at constant speed using a pump with stirring constant quantity delivery over a period of time

d fi

YQn £ *? / £ 3

en ti * C ^rt fSfIWSi

Temperature of 40 ⁰ C held reaction tank were introduced. The pH of the reaction solution was 1.0 and the PO ₄ -VZr molar ratio in this case was 1. The precipitate obtained was washed repeatedly with water until its pH was 3, after it had been left to stand for about 24 hours reached. The precipitate was then filtered, dried at 110 ⁰ C and was obtained as a product of zirconium phosphate.

2. After pulverizing the above zirconium

3b phosphate with a particle size of 2.4 to 1.7 mm, 15 ml of it were packed in a glass column, after which 1 1 of 0.1 N ammonia water containing 2 g of palladium chloride was passed through the glass column to carry out the ion exchange reaction. Then, the present ion-exchanged zirconium phosphate was thoroughly washed with water and reduced to a pre-drying at 110 ⁰ C with a stream of hydrogen for 8 hours at 400 ⁰ C while ammonia gas was removed, to obtain thereby zirconium phosphate, the palladium "vice halt 2.0 Was weight percent.

Catalytic converter 16

23.2 g of sodium hydroxide were dissolved in 3 l of water, then 48 g of phosphoric acid were added, after which 64.4 g of zirconium oxychloride in solution in 3 l of water were added, likewise with vigorous stirring. The pH of the aqueous solution at this point in time was 3.8 and the molar ratio PO ₄ -VZr was 2.0. The gel-like precipitate obtained was, after it had been left to stand for about 24 hours, filtered off, washed with water and ^{dried at 110 °} C. The dried precipitate was then treated with 0.1 N HCl to remove the chlorine ions, washed with water at HO ⁰ C dried and then the gel-like product obtained was comminuted to a particle size of 76 to 53 μ. Separately, 0.45 g

so dissolved palladium chloride in 10 ml of 28% strength ammonia water and then diluted with 200 ml of water 50 g of the dried gel-like product obtained above was then immersed in this solution and left to stand for 24 hours at room temperature. Then it was like in the production of the catalyst 16 continued to work, with zirconium phosphate having a content of 0.5 percent by weight Palladium was obtained.

catalyst

57 g of titanium tetrachloride were dissolved in 100 ml of 35% strength HCl solution and then diluted with 5 l of water. On the other hand, wufdcii 70 g of PhüsphofsüUfe with 5 l of water diluted. The two solutions were then mixed at room temperature with stirring, after which the The pH of the reaction solution was adjusted to 5.0 by slowly adding 28% strength ammonia water svurde. After stirring continued for an additional 4 hours, the solution was left for 24 hours place. The molar ratio P (V VTi at this point in time was 2.0. Thereafter, processing was as in the preparation of the catalyst 17 is a titanium phosphate catalyst obtained with a palladium content of 0.5 percent by weight.

catalyst

24 g of phosphoric acid and 12 g of caustic soda were dissolved in 500 ml of water. 41 g of hafnium were separated oxychloride dissolved in 500 ml of water. The latter solution was then mixed and added with the former solution Room temperature implemented. The pH of the react

Molar ratio PO4 - VHf was 2.0. Subsequently was as in the preparation of the catalyst 17, and a hafnium phosphate catalyst was obtained with a palladium content of 0.5 percent by weight.

The invention is explained in more detail below with the aid of examples. The determination of the alä The product obtained dimerized saturated ketones was carried out by Gasehromaiographi? Ancjerp.rsfiits was the palladium content of the catalyst by X-ray fluorescence analysis certainly.

Example 1 Dimerization and Saturation Reaction of Acetone

Catalysts 1 to 8 were used, and methyl isobutyl ketone (hereinafter abbreviated to MIBK) was prepared from acetone. 15 ml (about 15 g) of each of the catalysts listed in Table II were packed in the central part of a reaction tube 35 cm in length and 20 mm in diameter made of stainless steel. When the reaction of acetone was carried out in the presence of hydrogen under the reaction conditions shown in Table II, the following results were obtained. The pressure in all cases was the overpressure (kg / cm ² ), measured at the outlet end of the reaction tube. Abbreviations used in Table II, with the exception of MIBK. were IPA and DIBK, which mean isopropanol and diisobutyl ketone, respectively.

Tabel II Palladium- Catalyst no Reaction conditions water temperature pressure attempt salary Amount of material Used catalyst slip through lot Great (Weight tetem ketone percent) (l / h) Γ C) (kg / cm ² ) 0.5 1 (No. 1) (ml / h) 3 110 5.5 0.5 1 (No. 2) 60 4th 108 5.6 1 0.5 1 (No. 3) 60 6th 120 5.6 2 Zirconium phosphate 0.5 1 (No. 4) 30th 5 120 6.1 3 Zirconium phosphate 0.5 2 (No. 13) 30th 3 110 5.5 4th Zirconium phosphate 05 1 (No. 5) 60 4th 108 5.6 5 Zirconium phosphate 05 1 (No. 6) 60 3 110 55 6th Zirconium phosphate 05 1 (No. 7) 60 3 110 55 7th Zirconium phosphate 0.2 1 (No. 8) 60 4th 112 6.2 8th Zirconium phosphate 1.0 1 (No. 9) 60 4th 112 6.2 9 Zirconium phosphate 15th 1 (No. 10) 60 4th 112 62 10 Zirconium phosphate 05 3 60 4th 108 5.6 11th Zirconium phosphate 0.8 1 (No. 11) 60 3 120 6.1 12th Zirconium phosphate 0.4 1 (No. 12) 30th 3 120 6.1 13th Zirconium phosphate 2.0 4th 30th 3 108 5.7 14th Titanium phosphate 05 5 60 3 110 55 15th Hafnium phosphate 05 6th 60 3 110 55 16 Zirconium phosphate 05 7th 60 3 110 55 17th Zirconium phosphate 60 18th Titanium phosphate Hafnium phosphate

(Continuation) Conversion product selectivity By-product selectivity Great selectivity Space-time Results lung Great (Weight Great (Weight (Weight yield
on product attempt percent) percent) percent) (0/0) 96.2 0.6 DlBK. 3.0 (g / l / h) 15.3 MlBK. 95.8 IPA 1.0 DIBK 3.1 15.6 MIBK 74.8 IPA 24.0 - - 410 I. 18.7 MIBK 65.2 IPA 28.0 - - 2 23.6 MIBK 95.5 IPA - - - 3 14.0 MIBK 95.0 - - - - 4th 13.4 MIBK 96.4 - - - - - 5 15.0 MIBK 95.5 - - - - - 6th 14.6 MIBK OJ ₁ I. - 2.6 γμ ms
L / IUI \ I , U 7th * s> *
IU ₁ I. IVII LJIS. 92.3 ι η A-
ΙΓΑ 5.1 DIBK. 2.3 - 8th 17.8 MlBK. 91.1 IPA 6.5 DIBK. 2.0 - 3 17.0 MIBK. 92.7 IPA - - - - ok 12.0 MIBK 91.0 - i, 6 DIBK 5.6 - Xl 18.0 MIBK 94.3 IPA - - - 12th 14.0 MIBK. 91.0 - 3.4 DIBK. 5.3 - 13th 10.6 MIBK 95.7 IPA - - - - 14th 12.6 MIBK 93.5 - - - - - 15th 11.4 MIBK 94.0 - - - 16 10.0 MIBK - 17th 18th

Example 2
Dimerization and saturation reaction of acetone

MIBK was made from acetone using 15 ml of zirconium phosphate catalyst 1 using the same device as in Example 1 and changing the reaction temperature and the reaction pressure as well the charge quantities of acetone and hydrogen produced. The results obtained are in Table IH reproduced.

Table III Tempe
rature Overpressure acetone H ₂ Conversion
lung selectivity (o / o) DIBK. Space-time
yield
to MIBK attempt ("C) (kg / cm ² ) (ml / h) (l / h) (%) MIBK IPA 6.1 (g / l / h) 120 54 60 3 23.1 91 13th 5.4 570 1 112 5ß 60 3 16.3 93 1.2 24 410 2 102 54 60 3 143 97 0.5 5.9 380 3 114 5.6 60 4th 183 91.0 64 470 4th 114 5.6 75 5 153 93.4 0.8 5.8 480 5 114 5.6 105 7th 12.7 96.1 04 2a 580 6th 102 8.8 60 5 14.8 92.1 5.7 1.7 370 7th 102 7.6 60 5 15.1 943 4.0 2.4 390 8th 102 5.7 60 5 14.7 94.7 2.8 6.1 380 9 102 Z8 60 5 16.0 923 1.6 4.1 400 10 120 6.7 60 3 18.1 94.6 - 0.6 43 470 U 120 6.7 60 6th 19.2 92.6 1.0 6.8 480 12th 120 5.7 50 8th 22.4 8.0 480 13th 120 6.7 60 10 25.2 8Zl 93 560 14th

Example] 3

Dimerization and saturation reaction
various ketones

15 ml each of the catalysts 1, 11 and 12 were used packed in the central part of a reaction tube similar to that used in Example 2, and there were the reactions carried out between the different classes of ketones and hydrogen, the results shown in Table IV were obtained. Abbreviations used in Table IV represent the following connections:

MEK
DEK
MIBK
DNK

■ 5 MCK
APH
MHO
EMHO
TMNO

m ONHO
DCHB
PPPK

Methyl ethyl ketone,
Diethyl ketone,
Methyl isobutyl ketone, dinonyl ketone,
Methylcyclohexyl ketone, acetophenone,
3-Methy! Heptan-5-one, Ä

2,6,8-trimethylnonan-4-one,

11-octyl-12-nonylheneicosan-10-one,

2,4-DicycIohexyIbutan-4-one,

jS-phenyl-propyl phenyl ketone.

Table IV

Ver Used catalyst Great Kata Reaction conditions pressure hourly Results Around product Selek search Ketones lyser Tempe Fluid- HyKelon Wall activity No. rature keitsraum- lung Designation gischwin- tion age (Mol (IHSV) percent 942 (kg / cm-) (Ii ^:) (Molver- (%) 95.0 Zirconium phosphate 1 CC) 6.8 2.0 holding) 10.2 MHO 94.0 1 MEK Titanium phosphate 11th 145 6.8 2.0 0.2 10.0 MHO 96.5 2 MEK Hafnium phosphate 12th 145 6.8 2.0 0.2 7.7 MHO 96.0 3 MEK Zirconium phosphate 1 145 2.0 4.0 o-> 6.3 EMHO 82.2 4th DEK Titanium phosphate 11th 105 2.0 4.0 0.2 53 EMHO 84.0 5 DEK Zirconium phosphate 1 105 1.0 0.425 02 42.0 TMNO 85.3 6th MIBK Titanium phosphate 11th 202 1.0 0.425 1.1 38.5 TMNO 83.5 7th MIBK Zirconium phosphate 1 202 1.0 2.0 1.) 6.3 ONHO 86.0 8th DNK Titanium phosphate 11th 130 1.0 2.0 0.4 5.9 ONHO 82.0 9 DNK Hafiium phosphate 12th 130 1.0 2.0 0.4 4.0 ONHO 80.0 10 DNK Zirconium phosphate 1 130 1.0 2.0 0.4 6.5 DCHB 79.2 11th MCK Titanium phosphate 11th 130 1.0 2.0 0.2 6.0 DCHB 77.4 12th MCK Zirconium phosphate 1 130 1.0 1.0 0.2 4.7 PPPK 78.0 13th ΑΡΗ Titanium phosphate 11th 200 1.0 1.0 0.2 43 PPPK in the 14th ΑΡΗ Hafnium phosphate 12th 200 1.0 1.0 0.2 3.8 PPPK 15th ΑΡΗ Example 4 200 4> carried out. 0.2 by this KatE analyzers

Dimerization and saturation reaction
various ketones

15 ml each of the catalysts 16 to 18 were used, and the reactions between the various Classes of ketones and hydrogen were made

Central part of a reaction tube were packed according to that used in Example 1, the Results are shown in Table V. The abbreviations used in this table are same as in example 3.

Table V

Ver Ketones Catalyst used
search

Class no.

Reaction conditions

Tempe pressure
rature

hourly

Fluid-

keitsraum-

speed

digkeil

('C) (kg / cm') (h-'j

Results

H · Ketone Um- Product Conversion Be / eich Selek ming livitiit

(Molyer- (MoI-

ratio) (%) percent)

1 MEK zirconium phosphate 16 145 6.8 2.0 0.2 9.1 MHO

2 MEK titanium phosphate 17 145 6.8 2.0 0.2 8.5 MHO

3 MEK hafnium phosphate 18 145 6.8 2.0 0.2 7.0 MHO

4 DEK zirconium phosphate 16 105 2.0 4.0 0.2 6.0 EMHO

5 DEK titanium phosphate 17 105 2.0 4.0 0.2 5.2 EMHO

94.0 94.5 94.0 96.0 96.0 230 217/12

Ketones 17th No. 19th 22 755 pressure sliindlicfie 18th Results product Selek Fluid Around activity keitsraum- Wall Designation gesdnvin- Hj / ketone lung tion (Mol Forisei / iing age percent) Ver Used catalyst Reaction conditions 81.1 search Great Tempe (kg / cm- ¹ ) ι (h - ■) 85.4 16 rature 1.0 0.425 (%) TMNO 84.0 MIBK 17th 1.0 0.425 (Molver- 35.6 TMNO 83.0 MIBK 16 1.0 2.0 hälmis) 31.4 ONHO 83.0 DNK 17th 1.0 2.0 1.1 5.0 ONHO 82.0 DNK 18th 1.0 2.0 1.1 5.0 ONHO 80.0 DNK 16 '("C) 1.0 2.0 0.4 3.7 DChö 78.0 6th MCK Zirconium phosphate 17th 200 1.0 2.0 0.4 53 DCHB 75.0 7th MCK Titanium phosphate 16 200 1.0 1.0 0.4 5.0 PPPK 76.0 8th APH Zirconium phosphate 17th 130 1.0 1.0 0.2 4.0 PPPK 9 APH Titanium phosphate 18th 130 1.0 1.0 02 4.0 PPPK 10 APH Hafnium phosphate 130 02 3.5 11th Zirconium phosphate 130 0.2 Example 7 12th Titanium phosphate 130 02 13th Zirconium phosphate 200 14th Titanium phosphate 200 15th Hafnium phosphate 200 Example 5

Dimerization and saturation reaction of acetone and methyl ethyl ketone

4 ml of the catalyst 1 were in the middle part of a Pyrex reaction tube of 40 cm length and 12 mm Diameter packed, and then a mixture of acetone and methyl ethyl ketone in one 1: 1 molar ratio and hydrogen at rates of 1.7 and 5.8 ml / h, respectively, under the conditions introduced a reaction temperature of 175 ° C. The composition of the reaction product was as follows:

Dimerization and saturation reaction of acetone

acetone

Methyl ethyl ketone

Methyl isobutyl ketone

2-methylhexan-4-one

3-methylhexan-5-one

3-methylheptan-5-one

Diisobutyl ketone

2-methyl-4-ethylheptane

6-on

2,6,8-trimethylnonanone

and

rest

20.4 mole percent

29.9 mole percent

10.2 mole percent

9.7 mole percent

5.0 mole percent

3.1 mole percent 9.4 mole percent

6.6 mole percent

2.2 mole percent

3.5%

15 g of the zirconium phosphate catalyst prepared in accordance with paragraph (1) 16, which had been crushed to 2.4 to 1.7 mm, were in 50 ml of 1N HCl, in which 0.17 g Palladium chloride were dissolved, immersed. The zirconium phosphate was left in this for 24 hours State, and it was then dried under reduced pressure at 100 ° C, then subjected to a reducing treatment for 8 hours in a stream of hydrogen at 400 ° C, and a zirconium phosphate catalyst was obtained.

the palladium content of which was 0.7 percent by weight. 15 ml of this catalyst was packed in a reaction tube, and the reaction was carried out while introducing acetone and hydrogen at a rate of 60 ml / h and 4 l / h, respectively, under temperature conditions of 120 ° C. and pressure of 6.2 kg / cm ² carried out. A conversion of 16.0% and the following yields on a weight basis were obtained. MIBK 88.6%, IPA 53%. DIBK 2.0% and mesilyloxide 3.2%.

Examples 8 to »3
and Comparative Examples I to VI

Example 6

Dimerization and saturation reaction of acetone and diphenyl ketone

In an externally heated 300-ml autoclave were added 100 g of a diphenyl ketone / acetone mixture (Molverhällnis 9: 1) and 10 g of 1 Zirkonphosphatkatalysators eingebracht- After introduction of water 'fabric to a pressure of 5.0 kg / cm ² at Raumtcm * temperature, the reaction was carried out for 2 hours at 150 ° C. at a maximum pressure of 21 kg / cm ² . The product had the following composition in mole percent: densely converted diphenyl ketone 93%, unconverted acetone 2%, methyl isobutyl ketone 3% and 1.1 diphenylbutan'3-one 2%.

Experiments 8 to 13 listed in Table VI below were carried out under the conditions according to the invention and for comparison, experiments I to IV under the conditions according to German Auslegeschrift 12 60 454 and the experiments V and VI under the conditions according to the British Palentschrift 10 15 003 carried out.

1, manufacture of the catalysts

A. Preparation of the one used in the present invention
Catalyst

97 g of ZrOCIj · 8 H ₂ O were dissolved in 6 l of water and 0.50 g of PdClj were dissolved therein while the solution was heated. Separately, 35 g of HjPCm were dissolved in 6 water. Then the first solution gradually became the second

Solution added with stirring at room temperature. Concentrated aqueous ammonia was added to the resulting mixed solution until the ρ H value reached 4.8. The solution was stirred for a further 4 hours and then allowed to stand for 24 hours. The resulting precipitate was filtered off and washed with water. After removal of the unreacted salts from the residue that was obtained ⁰ C dried and a gel-like substance of zirconium phosphate at HO, which was replaced with palladium cations. The gel-like substance obtained had a molar ratio of PO-i-VZr of 1 and contained 0.5% by weight of Pd. The gel-like substance was pulverized to a size corresponding to a mesh size of 039 to 0.7 mm and ^{calcined for 8 hours at 400 °} C. in a stream of hydrogen, after which it was reduced in order to obtain the desired catalyst.

B. Preparation of the catalyst by the process
of the German interpretative document 12 60 454

A strong acidic cation exchange resin based on polystyrene-divinylbenzene of the sodium type (known as Dowex 50 WX 8) (see Chemielexikon Römpp, 6th edition, pp. 1595 and 1596) with a size corresponding to a mesh size of 0.83 to 0, 29 mm in an amount of 80 g (94 ml) was immersed in a wet state in 100 ml of 2N HCl for 3 hours at room temperature and then washed with ion-exchanged water. This procedure was repeated twice to make the resin H-type. Then 30 ml of a 2N HCl containing 2.0 g of palladium chloride were added and the water was evaporated off in vacuo on a water bath at 60 ° C. using a rotary evaporator. The dried resin obtained was packed in a quartz tube with an internal diameter of 20 mm and ^{treated for 27 hours at 100 °} C., with hydrogen gas flowing through it in an amount of 80 ml / min, in order to remove practically all of the remaining HCl in the catalyst. The catalyst obtained was black and weighed 43.1 g (47.2 ml).

C. Preparation of the catalysts according to
British Patent 10 15 003

C-1: Making one from palladium metal,
worn on ZrO ₂ . existing catalyst

100 g of zirconium oxychloride (ZrOCI ₂ · 8 H ₂ O) were dissolved in 21 of a water suitable for ion exchange. While stirring the solution well, ammonia water in a ratio of 1: 1 was gradually added to the solution to adjust the pH of the solution to 9.0. Stirring was continued for an additional 2 hours after the ammonia had been added and then the solution was allowed to stand for 24 hours. The precipitate was filtered off and washed. The Hydrogei obtained was dried for 12 hours at 120 ⁰ C, to form the Zirkonoxydgel. 50 g of the zirconium oxide gel were pulverized to a size of 0.15 to 0.074 itiiii and added to 50 ml of 1N * HCJ, which contained 0.4 g of palladium chloride in solution. With thorough stirring, this mass was subjected to evaporation on a water bath Powder was molded into pellets 5 mm in diameter and 3 mm in length, which were the desired catalyst.

C-2: Making one from palladium metal,

supported on Cai (PO ₄ ) 2, existing catalyst

39.0 g of calcium chloride (CaCl ₃ · 2 H ₂ O) (0.265 moles) was added to 750 ml of an ion exchange suitable

dissolved in water Separately, 14.6 g (0.149 mol) of 87% phosphoric acid and 28.2 ml (0.726 mol) of 28% NH ₄ OH were dissolved in 2100 ml of water. The first solution was added to the second solution to adjust the pH Set the value to 8.4. The precipitate obtained was left to stand for 24 hour, washed with water and then dried at 120 ⁰ C. 20 g of the dried gel were finely pulverized and added to 30 ml of an In-HCl which contained 0.17 g of palladium chloride in solution. While stirring well, the mass was subjected to evaporation on a water bath. The obtained product was molded into pellets having a size of 5 mm in diameter and 3 mm in length to obtain the desired catalyst.

2. Hydrogenative dimerization of acetone

2-1: Repetition of the experiments according to
jo present invention and according to

German interpretative document 12 60 454

Methyl isobutyl ketone was made from acetone under the reaction conditions listed in Table VI below using the catalyst according to the invention described above under A and of the catalyst described above under B prepared in accordance with German Auslegeschrift 12 60 454. The results are summarized in Table VI for Limen.

The reaction tube used in this experiment was made of stainless steel and had a length of 500 mm and an inner diameter of 10 mm. 15 ml of the catalyst were packed in its central part Reaction tube wound thermocouple determined.

2-2: Repetition of the experiments according to
British patent specification 10 15 003

A Pyrex reaction tube with an internal diameter of 20 mm and a length of 350 mm was charged in its central part with 5 ml of the catalysts obtained according to the method described above under CI and C-2 according to British patent specification 10 15 003. While hydrogen gas was being introduced into the reaction tube in an amount of 60 ml / min, the catalyst was reduced ^{at 300 ° C. for 6 hours.} The condensation and saturation conversion of acetone was then carried out under the reaction conditions listed in Table VI

3 <test results

Some of the experimental conditions in experiments 2 * 1 and 2 ^ 2 and the YersUcil results obtained are summarized in Table Vi below.

21 Tempe Daick 19th 22 755 Results 22nd IPA DIBK Space-time rature Around yield Table VI change by MIBK example from Selectivity ( ⁰ A) 1.9 1.2 hourly Mole acetone 1.8 4.7 Reaction conditions Space- relationship 1.6 33 (g / l cataly Kataly CQ (kg / cm ² ) fluidic Ha / acetone 0.6 1.8 sator / hour) sator 110 20th fast- (%} MIBK 1.8 7.5 604 130 20th ability (LHSV) 22.6 1.8 6.0 893 130 20th (Std .->) 34.6 1678 130 20th of acetone 25.6 96.9 5.1 4.9 2442 8th 140 20th 4th 0.30 18.4 93.5 4.5 4 5 1056 S. 140 20th 4th 030 42.2 95.1 7.8 2.8 2098 10 A ») 10 0.31 33.4 96.1 14.3 1.9 11th A. 130 20th 20th 0.30 90.7 - - 688 12th A. 130 20th 4th 0.28 25Y 91.2 _ 715 13th A. 110 6th 10 0.32 173 303 comparison A. 110 20th 12.5 90.0 314 I *) A. 200 1 4th 0.30 13.6 91.0 _ i: 200 1 6th 0.30 1.0 87.9 _ III B **) 4th 0.30 0.5 83.6 IV B. 4th 030 <50 V B. 2 0.40 VI B. 2 0.40 C-I ***) C-2

*) Catalyst A: Catalyst according to the invention, prepared according to (I) -A.
**) Catalyst B: Catalyst according to German Auslegeschrift 12 60454. manufactured according to (I) -B.

· * ■ *) Catalyst CI and C-2: Catalysts manufactured according to British patent specification 10 15003 ns.-h (I) -CI and (I) -C-2. LHSV of acetone: liquid volume / catalyst volume / hour of acetone;
MIBK: methyl isobutyl ketone;
IPA: isopropyl alcohol;
DIBK. Diisocyanate ketone;
Space-time yield of MIBK: Yield of MIBK in grams per liter of catalyst per hour.

In the examples 9 to 13 according to the invention carried out at 130 to 140 ⁰ C and a pressure of 20 kg / cm ² , the excellent result is shown that the methyl isobutyl ketone in a space-time yield of about 1000 to 2400 from acetone in an amount of 4 to 20 (liquid hourly space flow rate [LHSV]) could be obtained.

In contrast to this, under appropriate conditions according to the method of German Auslegeschrift 12 60 454, the space-time yield of methyl butyl ketone is 688 g / IC / otalysator / hour. and the conversion of acetone 25.3% when the reaction temperature is 130 ⁰ C. the reaction pressure is 20 kg / cm ² and

the amount of acetone (LHSV) is 4.0, while when the amount of acetone (LHSV) is 6.0, the Space-time yield of methyl tsobu'yl ketone 715 g / l catalyst / hour. is and the conversion of acetone

4n is only 17.3%.

The amount of acetone (LHSV), the conversion of acetone and the space-time yield of methyl isobutyl ketone in Examples 9, 10 and 11 under the conditions according to the invention and in the tests I and II (German Ausiegeschriit 12 60 454) are in the following Table VIi summarized for easier comparison.

Table VII lot
of acetone
(LHSV) conversion
of acetone
(O / o) Space-time
Exploitation
to MIBK example 4th 34.6 893 9 10 25.6 1678 10 20th 18.4 2442 11th comparison 4th 25.3 688 I. 6th 17.3 715 II

With regard to the values from Table VI, there is 65 acetone 20, a conversion of acetone which

to indicate that, according to the conditions, the present is comparable to that in which it is obtained,

lowing invention (Examples 9, 10 and 11) even if if the hourly space air velocity

the hourly space velocity of acetone is 6 (test 11) in the process

German Auslegeschrift 12 60 454 is received so that the space-line yield (g / l catalyst / Sld.) of MIBK is therefore very high.

A comparison of the catalysts of the invention with those of British Palentschrift 10 15 003

and the German Auslegescl-rifl 12 60 454 thus results in As can be seen from Tables VI and VII, with the same procedural amendments, the clear superiority is achieved of the catalysts of the invention.

Claims (1)

Claim: Process for the production of dimerized, saturated ketones by dimerizing a ketone the group consisting of A. at least one ketone which contains at least one hydrogen atom in cc or in α and cc 'positions to the carbonyl group, or B. the mixture of a) a ketone with at least two hydrogen atoms bonded to either one or both of the carbonyl group adjacent carbon atoms and b) a ketone which does not contain a hydrogen atom on the carbon atoms bonded to the carbonyl group, in the presence of hydrogen on metallic palladium Catalysts at elevated temperature, characterized in that the reaction is carried out at a temperature of 80 to 250 ° C and a pressure of 1 to 50 kg / cm ² in the presence of a Kalaiysaiors, the active ingredient a ') a phosphate of at least one of the metals zirconium, titanium and hafnium and b ') 0.1 to 5.3 percent by weight of metallic palladium, based on the metal phosphate deposited on this phosphate. contains. 10