Method for catalytic decomposition of c6-c12-cycloalkyl hydroperoxides

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic decomposition of organic hydroperoxides representing important compounds on organic synthesis. Decomposition of cycloalkyl hydroperoxides comprising from 6 to 12 carbon atoms results to formation a mixture of corresponding alcohols and ketones. Process is carried out in the presence of a solvent (alkane, halogen-containing hydrocarbon) at temperature from 20°C to 200°C. Catalyst comprises ruthenium as a catalytically active metal added to a solid carrier chosen from the following group: carbon prepared by pyrolysis of acetylene and metal oxides chosen from the group comprising zirconium, aluminum, lanthanum and manganese. The amount of catalyst expressed as the mole percents of ruthenium to the amount of moles of hydroperoxide to be decomposed is from 0.0001% to 20%. Preferably, the catalyst comprises one additional rare-earth element as a component of alloy. The carrier represents, as a rule, metal oxide with high specific surface above 10 m2/g but preferably, above 100 m2/g that is resistant against oxidation. The hydroperoxide concentration is in the range from 1 to 80 wt.-% with respect to the solution mass. Preferably, hydroperoxide represents cyclohexyl, cyclododecyl, tetraline, ethyl benzene or pinane hydroperoxide and hydrocarbon used in preparing the parent hydroperoxide is used as a solvent. Invention provides the development of the modified catalyst enhancing conversion and selectivity in decomposition of hydroperoxides.

EFFECT: improved method for decomposition.

8 cl, 24 ex

 

The present invention relates to a method of decomposition of organic hydroperoxides in the presence of a catalyst.

Organic hydroperoxides are important intermediate compounds in the production of alcohols, ketones and acids are often employees of the parent compounds in organic synthesis.

Among the above-mentioned organic hydroperoxides hydroperoxide of cyclohexyl obtained by oxidation of cyclohexane. The catalytic decomposition it leads to cyclohexanone and cyclohexanol. These latter compounds can be converted to adipic acid by oxidation. Adipic acid is an important intermediate chemical compound used in the manufacture of many polymers, such as, for example, polyamides, polyurethanes. This connection may have numerous other applications.

The decomposition of organic hydroperoxides, in particular cumene cyclohexyl (GPCG) (HPOCH), can be carried out primarily by means of homogeneous catalysis, i.e. in the presence of a catalyst dissolved in the reaction medium. Thus, in the patent FR-A-1580206 described oxidation cycloalkane in the liquid phase, followed by heating the thus obtained solution of cumene cycloalkyl in cycloalkene in the presence of soluble derivative chrome is as a catalyst. Also in an article in Journal of Molecular Catalysis (1988), 48, p. 129-148 described the use of organic salts, such as octanoate cobalt, or complex compounds dissolved in the liquid organic phase in which the reaction takes place.

However, the use of such inexpensive salts is inconvenience, because the catalysts are quickly deactivated, causing the loss of them in the sediment in the environment.

To resolve these problems were proposed more complex catalytic systems, such as complexes between metal and porphyrins or phthalocyanines. Such systems are described, for example, in patent US 5672778 and in articles published in "Catalysis Letters" 20, 1993, 359-364 or 36, 1996, 69-73. Similarly, complex compounds based on cobalt and similar ligands have also been described in an article published in the Journal of the American Chemical Society (1985), 107, p. 3534-3540.

It was also suggested that, in particular, in the European patent 270468 the use of ruthenium and ligand based on 1,3-bis(2-aminopyridin)isoindoline.

Mentioned catalytic systems are inconvenience, in particular, their stability (oxidation resistance), their complexity makes them malaconotinae.

It was also proposed to carry out the decomposition of the hydroperoxide by means of heterogeneous catalysis, i.e. in the presence of a catalyst, dissolved in Rea the operating environment. However, these catalysts often have a rapidly decreasing activity, and mentioned the loss of activity occurs, for example, due to the leaching of the catalytic phase.

In addition, they also proposed catalysts, allowing, simultaneously with the decomposition of the hydroperoxide to alcohol and/or ketone, to carry out the oxidation of the hydrocarbon used as solvent, giving thus the opportunity to improve the overall yield of the conversion of hydrocarbon to alcohol and ketone. Specified oxidation is called in the art "oxidative transfer". It is the transfer of one of the oxygen atoms of the hydroperoxide to the hydrocarbon to obtain the corresponding alcohol. European patent 0331590 describes the use of homogeneous catalysts based on complexes of osmium, which allows to obtain oxidative transfer of the order of 40%.

The present invention aims to propose a new, economically interesting, heterogeneous catalytic system, allowing, in particular, to obtain a high level of oxidative migration.

More precisely, the method of decomposition of organic hydroperoxides in the presence of a catalyst to a mixture of alcohols and ketones, in which the catalyst contains at least one catalytically active metal element based on ruthenium, put in a solid the first carrier, selected from the group consisting of oxides of metals and coal, such as coal, obtained by pyrolysis of organic compounds.

The catalyst according to the invention is a heterogeneous catalyst, which can be obtained all the usual methods of making catalysts, called catalysts on the media. Thus, the term "introduced", used above, covers all forms of communication between the carrier and a compound or complex, or compounds or complexes of ruthenium. Thus, this term includes not only the adsorption of ruthenium compounds on the carrier, but also the co-deposition of ruthenium and predecessor of the media. Ruthenium may be simply deposited on the surface of the carrier, in particular on the surface, at least some of the pores of the support, or, on the contrary, associated with the above-mentioned electronic media connections.

Carriers suitable for the invention preferably have a high specific surface and resistant to oxidation. The metal oxides having a specific surface area greater than 10 m2/g, mostly more than 100 m2/g, are carriers preferred for the invention.

As carriers suitable for the invention include oxides of aluminum, oxides of rare earth metals such as the oxides of cerium or lanthanum, zirconium oxide, magnesium oxide and silicon dioxide, and various coals, preferably with a high specific surface, such as, for example, acetylene black.

The catalyst according to the invention may also contain other metal elements, which allows to improve or stimulate the catalytic activity of ruthenium. As metal elements suitable for use as alloying additives, can be called transition metals, such as metals belonging 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8 groups of the Periodic system of elements, such as published in the Handbook of Chemistry and Physics, 66émeédition (1985/1986), The Chemical Rubber Co.

More specifically include titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, Nickel, rhodium, palladium, platinum, iridium, osmium, copper, silver, gold and rare earth metals such as lanthanum and cerium.

The decomposition reaction according to the invention is carried out in the liquid phase, the concentration of hydroperoxide in the reaction medium is in the range from 0.1 to 80 wt.%. Preferably the concentration is in the range from 0.5 to 20 wt.%.

You can use various solvents, such as alkanes, among which, more specifically referred to as hexane, heptane and isooctane; cycloalkanes, among which illustrate mention cyclohexane and cyclooctane; the aroma is practical hydrocarbons, such as benzene, toluene and xylene; halogenated hydrocarbons, and mixtures of the above solvents.

However, it should be noted that as the hydroperoxide occurs typically in the form of a solution in a hydrocarbon, such as cyclohexane, as a result of its oxidation decomposition reaction is preferably carried out with a solution resulting from the oxidation of hydrocarbon (cyclohexane), in which the concentration of the hydroperoxide is within the limits specified above. This solution can be used in that condition, as is, or after removal of some components in a way that is itself known. You can also use the solution of the hydroperoxide in a solvent, such as essentially pure cyclohexane.

The amount of catalyst can vary widely, in particular, depending on the conditions of the method: the process runs continuously, periodically or semi-continuous. Usually, the amount of catalyst, expressed as the molar percentage content of active metal in relation to biodegradable hydroperoxide, from 0.0001 to 20%, preferably from 0.01 to 10%.

As part of the continuous process it is obvious that the amount of catalyst relative to the hydroperoxide does not matter and that the ratio mentioned before, can t the com case to be much more important.

The temperature is usually in the range of from 20 to 200°C, preferably from 80 to 130°C.

Atmospheric pressure or the pressure more than atmospheric will be enough to support the cyclohexane in the liquid phase.

The time of reaction (or stay) is usually from several minutes up to 4 hours and can be adjusted to fit the objectives of production, the number of different components used catalytic system and other parameters of the reaction.

Upon completion of the reaction products can be isolated and/or separated in any suitable way, for example by distillation.

The hydroperoxides, which are used in the method according to the invention, are typically the primary or secondary hydroperoxides derived from alkanes, cycloalkanes, alkylaromatic hydrocarbons, aromatic cycle, which may contain one or more substituents, such as, in particular, alkyl group or halogen atom, more specifically, a chlorine atom, alkenes and cycloalkenes containing from 3 to 20 carbon atoms.

As examples of such hydroperoxides can be called the hydroperoxide of cyclohexyl, hydroperoxide of cyclododecyl, the hydroperoxide of tetralin, ethylbenzene hydroperoxide, the hydroperoxide of Pinna.

Among these hydroperoxides one of the most titbits what x is, clearly, the hydroperoxide of cyclohexyl, oxidation of which leads to cyclohexanol and cyclohexanone, the intermediate products in the adipic acid production, one of the starting compounds for polyamide 6-6.

The examples below are only for information that will illustrate the invention and its advantages and details.

Example 1:Synthesis of catalyst A (EN/ZrO2- 5 wt.% EN)

Based media ZrO2pre-calcined for 2 hours at 500°C. After calcination of zirconium dioxide (10 g) was placed in 500 ml of water and kept under stirring for 5 minutes at ambient temperature. The pH value of the solution is brought to pH 9 by addition of Na2CO3. Then the temperature was raised with stirring. Then add an aqueous solution of RuCl3.nH2O supplied in the sale of the company "STREM" (about 20 ml by 1.79 g RuCl3.nH2O)at 90°C for 20 minutes. The mixture was kept under stirring for 15 minutes. Again bring the pH up to 8/9 addition of Na2CO3and stirred the solution for 3 hours at 90°C.

The mixture is then cooled to 40-50°and then filtered. The precipitate is subjected to the operations of filtration-washing with water until neutral pH of the wash water. The solid is dried for 18 chaitri 120° C and then calcined at 400°within 2 hours.

Example 2:Synthesis of catalyst (Ru/acetylene soot Y200 - 5 wt.% EN)

Media Y200 (media acetylene soot comes to the sale of the company SN2A)pre-calcined for 1 hour at 500°C. After the annealing acetylene carbon black (10 g) was placed in 500 ml of water and kept under stirring for 5 minutes at ambient temperature. The pH value of the solution is brought to pH 9 by addition of Na2CO3. Then the temperature was raised with stirring. Then add a solution of RuCl3in water (about 20 ml by 1.79 g RuCl3), at 90°C for 20 minutes. The mixture was kept under stirring for 15 minutes. Again bring the pH up to 8/9 addition of Na2CO3and stirred the solution for 3 hours at 90°C.

The mixture is then cooled to 40-50°and then filtered. The precipitate is subjected to the operations of filtration-washing with water until neutral pH of the wash water. The solid is dried for 18 hours at 120°and then calcined at 400°within 2 hours.

Example 3:Synthesis of catalyst C (EN/acetylene soot Y200 - 5 wt.% EN)

Media Y200 pre-calcined for 1 hour at 500°s on the air. After ignition of acetylene carbon black (10 g) was placed in 300 ml of THF and maintained at Pere is eshiwani for 30 minutes at ambient temperature. Then add a solution of Ru3(CO)12in tetrahydrofuran (THF) (100 ml 1.12 g Ru3(CO)12)at ambient temperature for 30 minutes. The mixture was kept under stirring for 30 minutes. Then the solution is placed in a rotary evaporator for 4 hours (ambient temperature, atmospheric pressure, 200 rpm). Then THF is evaporated at 20 mm Hg. Obtain 11 g of solid substance.

Example 4:Synthesis of catalyst D (Ru/alumina and 5 wt.% EN)

The carrier of aluminum oxide provided on sale firm Condéa pre-calcined for 6 hours at 750°C. After calcination, the alumina (10 g) was placed in 500 ml of water and kept under stirring for 5 minutes at ambient temperature. The pH value of the solution is brought to pH 9 by addition of Na2CO3. Then the temperature was raised up to 90°45 minutes) with stirring. Then add a solution of RuCl3in water (about 20 ml 1.98 g RuCl3), at 90°C for 20 minutes. The mixture was kept under stirring for 15 minutes. Again bring the pH up to 8/9 addition of Na2CO3and stirred the solution for 3 hours at 90°C.

The mixture is then cooled to 40-50°and then filtered through a glass filter No. 4. The precipitate is extracted into 100 ml of water at 40-50°C. followed by 4 stage filtration-about Yuki water until neutral pH of the wash water. The solid is dried for 24 hours at 120°without calcination.

Example 5:Synthesis of catalyst E (EN/La2O3- 5 wt.% EN)

The carrier oxide lanthanum (included in the sale by the company Rhodia) first subjected to pre-treatment. This last is the location of lanthanum oxide in water (90 ml) for 30 minutes with increasing temperature (up to 90°3 hours). Then the solution is cooled to 45°, filtered, dried for 18 hours at 120°C, then calcined at 400°C for 24 hours in air (5°C/min). After annealing the oxide of lanthanum (10 g) was placed in 500 ml of water and kept under stirring for 5 minutes at ambient temperature. The pH value of the solution is brought to pH 9 by addition of Na2CO3. Then the temperature was raised up to 90°45 minutes) with stirring. Then add a solution of RuCl3in water (about 20 ml, 1.08 g RuCl3), at 90°C for 20 minutes. The mixture was kept under stirring for 15 minutes. Again bring the pH up to 8/9 addition of Na2CO3and stirred the solution for 3 hours at 90°C.

The mixture is then cooled to 40-50°and then filtered through a glass filter No. 4. The precipitate is extracted into 100 ml of water at 40-50°C. followed by 4 stage filtration-washing with water until neutral pH of the wash water. TV is Joe substance dried for 16 hours at 120° With no ignition.

Example 7:Synthesis of catalyst F (Ru/magnesium oxide and 5 wt.% EN)

The carrier of magnesium oxide (UBE Industrie 100 (E) (10 g) is first subjected to pre-treatment. This last is the premise of magnesium oxide in water (100 ml) for 30 minutes with increasing temperature (up to 90°3 hours). Then the solution is cooled to 45°, filtered, dried for 16 hours at 120°in an oven, and then calcined at 400°C for 24 hours in air (5°C/min). Pre-treated magnesium oxide are placed in 400 ml of water and kept under stirring for 5 minutes at ambient temperature. The pH value of the solution is brought to pH 9 by addition of Na2CO3. Then the temperature was raised up to 90°45 minutes) with stirring. A solution of RuCl3in water (about 20 ml, 1.08 g RuCl3) add at 90°C for 20 minutes. The mixture was kept under stirring for 15 minutes. Again bring the pH up to 8/9 addition of Na2CO3and stirred the solution for 3 hours at 90°C.

The mixture is then cooled to 40-50°and then filtered through a glass filter No. 4. The precipitate is extracted into 100 ml of water at 40-50°C. followed by 4 stage filtration-washing with water until neutral pH of the wash water. The solid is dried for 16 hours at 120°without calcination.

Example 8:Synthesis of catalyst G (EN/magnesium oxide and 5 wt.% EN)

The carrier of magnesium oxide (UBE Industrie 100 (E) (15 g) first subjected to pre-treatment. This last is the premise of magnesium oxide in water (150 ml) for 30 minutes with increasing temperature up to 90°With 3 hours. Then the solution is cooled to 45°, filtered, dried for 16 hours at 120°in an oven, and then calcined at 400°C for 24 hours in air (5°C/min). Pre-treated magnesium oxide are placed in 150 ml of water and kept under stirring for 10 minutes at ambient temperature. Then add a solution of RuCl3in water (about 20 ml 1.62 g RuCl3) at ambient temperature for 15 minutes. The mixture was kept under stirring for 1 hour 30 minutes at ambient temperature. After decanting the water are removed in a rotary evaporator at 20 mm Hg at 50°C. the Precipitate is dried in an oven for 16 hours at 120°C. Then to the precipitate on the filter type 41 ml of 0.1 M NaOH to be able to mix. The resulting solution was heated at 95°C for 3 hours. Add 50 ml of 0.1 M sodium hydroxide solution and allow the solution to cool to 40-50°C. After two washes with 100 ml of water at 45°the solid is dried for 16 hours at 120°in a drying Cabinet. Finally, the solid substances is CTB pull in 400 ml of water at ambient temperature, stirred for 30 minutes, heated at 70°C for 3 hours, then centrifuged (pH of the aqueous phase equal to 7) at 3500 rpm for 20 minutes. The thus obtained solid substance is dried 16 hours at 120°C.

Example 9:Synthesis of catalyst H (EN/acetylene soot Y70 (SN2A) - 5 wt.% EN)

Media acetylene soot Y70 SN2A (10 g) is first calcined for 1 hour at 500°C. carbon Black (10 g) was placed in 400 ml of water and kept under stirring for 15 minutes at ambient temperature. The pH value of the solution is brought to pH 9 by addition of Na2CO3. Then the temperature was raised up to 90°45 minutes) with stirring. Then add a solution of RuCl3in water (about 20 ml, 1.08 g RuCl3), at 90°C for 20 minutes. The mixture was kept under stirring for 15 minutes. Again bring the pH up to 8/9 addition of Na2CO3and stirred the solution for 3 hours at 90°C.

The mixture is then cooled to 40-50°and then filtered through a glass filter No. 4. The precipitate is extracted into 100 ml of water at 40-50°C. followed by 4 stage filtration-washing to obtain a neutral pH of the wash water. The solid is dried for 16 hours at 120°without calcination.

Example 10:Synthesis of catalyst J (EN/Carin (HSA5) - 5 wt.% EN)

Media zerin HSA5 (included in the sale by the company Rhodia (10, g) is first calcined 6 hours at 500° With on the air. The cerium oxide (10.2 g) was placed in 100 ml of water and then when the ambient temperature is added to the anhydrous solution of Ru(acac)3in acetone (100 ml per 2 g of Ru(acetylacetonate)3). The mixture was kept under stirring for 2 hours at ambient temperature. The solution was concentrated in a rotary evaporator at 45°With, then dried for 16 hours in a drying Cabinet at 120°C. To dry the precipitate is then added 41 ml of 0.1 M sodium hydroxide and heated under stirring for 3 hours at 95°C. After cooling to 40-50°the product is filtered, then washed 4 times with 100 ml of water at 45°C. the Solid is dried for 16 hours at 120°in a drying Cabinet. Then the solid is extracted in 210 ml of water at ambient temperature, then heated for 3 hours at 70°C. After cooling to 45°the solid is filtered, then dried for 16 hours at 120°C.

Example 11:Synthesis of catalyst K (Ru, Fe doped, on acetylene soot Y200)

Media Y200 SN2A (10 g) calcined 1 hour at 500°C. Acetylene carbon black (10 g) was placed in 400 ml of water and stirred for 5 minutes. The mixture is gradually brought up to 90°With (45 minutes) and a solution of FeCl3.2H2O (0,509 g in 50 ml water) is added to acetylene soot at 90°for 13 minutes. The pH value of the solution was adjusted to 5.5 by adding sodium bicarbonate. The solution under eribaum 30 minutes under stirring at 90° C. After cooling to 45°perform 4 consecutive washing with 100 ml of water at 45°C. the Product is dried in an oven for 16 hours at 120°C. the Solid is again placed in a reactor in the presence of 400 ml of water, heated to 90°and bring the pH to 10 with the help of Na2CO3. Maintain stirring for 1 hour at 90°C. and Then for 20 minutes at 90°add a solution of RuCl3ALPHA in water (approximately 20 ml 1.08 g RuCl3). The mixture was kept under stirring for 3 hours at 90°C. After cooling to 40-50°the product is filtered, then 4 times consecutively washed and filtered in order to obtain a neutral pH value of wash water. The solid is dried for 16 hours at 120°in a drying Cabinet.

Example 12:Synthesis of catalyst L (Ru alloyed Co, acetylene soot Y200)

Media Y200 SN2A (10 g) calcined 1 hour at 500°C. Acetylene carbon black (10 g) was placed in 400 ml of water and stirred for 5 minutes. The mixture is gradually brought up to 90°With (45 minutes) and add sodium bicarbonate to reach pH 10. Then for 20 minutes at 90°add a solution of RuCl3ALPHA in water (approximately 20 ml 1.08 g RuCl3). The mixture was kept under stirring for 1 hour at 90°C. Then the reactor at 90°add a solution of CoCl2.6H2O (1,429 g in 20 ml in the water). The solution supports 1 hour under stirring at 90°C. After cooling to 45°the solid is filtered through a glass filter No. 4. The precipitate is again placed in 100 ml of water at 40-50°and perform 4 consecutive washing in order to obtain a neutral pH of the wash water. The solid is dried for 16 hours at 120°in a drying Cabinet.

Examples 13-24: the Results of catalytic decomposition of cumene cyclohexyl (GPCG)

Catalysts on carriers were tested under normal conditions of decomposition of hydroperoxides: 40 g of the oxidation product formed during avtookislenie cyclohexane (5% GPCG, as described in the patent FR2087375), placed in the presence of approximately 170 mg of heterogeneous catalyst for several hours in the reactor Dean stark at 80°With continuous removal of water formed in the reaction medium). The catalysts (5 wt.% Ru) were used with the molar relationship EN/GPCG=0,5%. Quantitative determination of residual GPCG was carried out by reverse potentiometric titration (iodine/thiosulfate), quantitative determination of cyclohexanol (ol) and cyclohexanone (he) - method GC (CPG). The results are shown in the table following. Under the JV (degree of conversion) understand the ratio of the number of moles turned GPCG to the number of moles of the original GPCG.

Ceren
ExampleCatalyst No.MetalMediat (min)SP (%)he/ol
Example 13AENThe Zirconia6097,4/
Example 14BENAcetylene black Y2005097,70,52
Example 15CENAcetylene black Y2006097,30,55
Example 16DENAluminium oxide90to 97.10,52
Example 17EENThe oxide of lanthanum6097,70,52
Example 19FENMagnesium oxide270of 97.80,53
Example 20GENMagnesium oxide300for 95.30,53
Example 21HENAcetylene black Y7011093,50,48
Example 22JEN4597,90,63
Example 23KRu/FeAcetylene black Y2009095,80,48
Example 24LEN/CoAcetylene black Y20012094,50,47

1. The method of decomposition of cycloalkylcarbonyl containing 6 to 12 atoms, alcohols and ketones in the presence of a catalyst and a solvent, wherein the process is carried out at a temperature of from 20 to 200°With the catalyst as a catalytically active metal contains ruthenium, put in a carrier selected from the group consisting of carbon, obtained by the pyrolysis of acetylene, and oxides of metals selected from the group comprising zirconium, aluminum, lanthanum, manganese, and the amount of catalyst, expressed in molar percent of ruthenium relative to the number of moles degradable hydroperoxide, from 0.0001 to 20%.

2. The method according to claim 1, wherein the carrier is selected from the group consisting of oxides of metals having a specific surface area greater than 10 m2/g, preferably greater than 100 m2/year

3. The method according to claim 1 or 2, characterized in that the catalyst contains at least one additional metal as alloying element

4. The method according to claim 3, wherein the alloying metal is selected from the group consisting of rare earth metals, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, Nickel, rhodium, palladium, platinum, gold, silver, copper, iridium, osmium.

5. The method according to claim 1, characterized in that the solvent is a hydrocarbon, alkane, halogenated hydrocarbon or a mixture of these solvents.

6. The method according to claim 5, characterized in that the solvent is a hydrocarbon, identical to the hydrocarbons, the oxidation of which leads to the hydroperoxide to be decomposition.

7. The method according to claim 1, characterized in that the concentration of hydroperoxide is in the range from 1 to 80% relative to the weight of the solution.

8. The method according to claim 1, wherein the hydroperoxide is selected from the group consisting of a hydroperoxide of cyclohexyl, hydroperoxide of cyclododecyl, the hydroperoxide of tetralin, ethylbenzene hydroperoxide, the hydroperoxide of Pinna.



 

Same patents:

FIELD: organic chemistry, in particular production of carbonyl compounds such as aldehydes and ketones.

SUBSTANCE: claimed method includes reaction of nitrous oxide with alkenes in presence of inert gas as diluent. Reaction is carried out in gas phase at 401-700°C and under pressure of 2-300 atm. Target compounds represent value intermediates for precise and base organic synthesis.

EFFECT: method of high selectivity in relation to target products and improved explosion proofing.

5 cl, 1 tbl, 14 ex

The invention relates to an improved method for producing a mixture of ketones/alcohols using decomposition cycloalkylcarbonyl in the presence of a catalyst containing a catalytically active metal element is immobilized on a solid carrier, and the catalyst obtained by the fixation of ORGANOMETALLIC compounds of General formula III or IIIa:

,

,

in which M denotes a metal ion, or a combination of metal ions, corresponding to the elements belonging to group IB-VIIB or VIII of the Periodic table (CAS version), including the lanthanides; m is an integer from 1 to 6; p denotes an integer from 0 to 4; q represents an integer from 1 to 4; X represents an anion

The invention relates to the production of cyclohexanone by liquid-phase oxidation products of hydrogenation of benzene containing cyclohexene, nitrous oxide or its mixture with an inert gas

The invention relates to a method for producing cyclohexanone, which is based on the reaction of liquid-phase oxidation of cyclohexene to cyclohexanone nitrous oxide or its mixture with an inert gas

The invention relates to the dehydrogenation of secondary alcohols, more particularly to a method and catalyst for the dehydrogenation of cyclic secondary alcohols and process for the preparation of this catalyst

The invention relates to a method for producing oxidation products of cyclohexane catalytic liquid-phase oxidation of oxygen-containing gases

The invention relates to an improved process for the preparation of cyclohexanone (Chona), which is an intermediate for the synthesis of caprolactam

The invention relates to a method of obtaining a mixture containing cyclic saturated alkane and the corresponding alkanol

The invention relates to a method for producing ketones, in particular to a method for producing ketones using reaction paired diolefines and water, and thus obtained ketones

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing phenol and acetone by acid-catalyzed cleavage of cumyl hydroperoxide. Method involves preliminary heating the reaction mixture to temperature above 100°C and then for thermal treatment of product heat in exothermic reaction is used, mainly the cleavage reaction of cumyl hydroperoxide that presents in the concentration from 5 to 10 wt.-%. The preferable residual content of dicumyl hydroxide in thermally treated product is 0.01-0.05 wt.-%. Stages in cleavage of cumyl hydroperoxide and the following thermal treatment can be carried out in a single reactor with two zones among that one zone is fitted with a device for heat removing and another zone has a feature of the flow-type pipe. Reactor is equipped by a device for circulation of part of product from thermal treatment zone to a feeding line for decomposition of product. Method provides improving energetic indices of process due to optimal consumption of heat energy in maintaining high selectivity of the decomposition process.

EFFECT: improved preparing method.

15 cl, 3 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.

EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.

11 cl, 1 dwg, 9 ex

The invention relates to an improved method of decomposition of the hydroperoxide with the formation of a mixture containing the corresponding alcohol and ketone, comprising the stage of: a) adding water in the amount of 0.5-20% in the mixture containing the hydroperoxide; (b) the deletion of specified volume of water in such a way that together with water removes water-soluble impurities; C) removing the remaining water in such a way that the reaction mixture is not more than 2% of water; and (d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous catalyst containing gold, supported on a carrier

The invention relates to an improved method for producing a mixture of ketones/alcohols using decomposition cycloalkylcarbonyl in the presence of a catalyst containing a catalytically active metal element is immobilized on a solid carrier, and the catalyst obtained by the fixation of ORGANOMETALLIC compounds of General formula III or IIIa:

,

,

in which M denotes a metal ion, or a combination of metal ions, corresponding to the elements belonging to group IB-VIIB or VIII of the Periodic table (CAS version), including the lanthanides; m is an integer from 1 to 6; p denotes an integer from 0 to 4; q represents an integer from 1 to 4; X represents an anion

-methylstyrene" target="_blank">

The invention relates to an improved method for production of phenol, acetone and-methylstyrene Kukolnik method and relates to the stage of acid decomposition of technical cumene hydroperoxide
The invention relates to the production of cycloalkanones C8-C12promising intermediates in the synthesis of lactams, aliphatic dicarboxylic acids, Daminov - monomers for the production of polyamide fibers, plastics and plasticizers new types and other valuable materials

The invention relates to the production of phenol and acetone by decomposition of technical cumene hydroperoxide (CHP)

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.

EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.

11 cl, 1 dwg, 9 ex

Up!