A method of producing mixtures of alcohols to ketones

 

(57) Abstract:

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. More specifically the invention relates to the production of a mixture of cyclohexanol/cyclohexanone decomposition of gidroperekisi of cyclohexyl in the presence of heterogeneous catalysis. The method allows an increased cycle length and lifetime of the catalyst to obtain a mixture of the alcohol/ketone, not containing or containing a very small admixture of metal. 5 C.p. f-crystals, 2 tab.

The invention relates to a method for producing mixtures of alcohols with ketones razloga the/cyclohexanone decomposition of gidroperekisi of cyclohexyl in the presence of heterogeneous catalysis.

Of these organic hydroperoxides Gidropress of cyclohexyl obtained by oxidation of cyclohexane. Catalytic decomposition of gidroperekisi of cyclohexyl gives cyclohexanone and cyclohexanol.

the cyclohexanol/cyclohexanone efficiency are very important because they open the way to the production of high-value chemical products such as adipic acid. These methods are described in the extensive literature: as in scientific articles and patents.

Classic industrial method consists in the oxidation of cyclohexane with air, allowing to obtain a mixture of compounds, which include Gidropress of cyclohexyl (GPCG), alcohols, ketones and acids. Gidropress of cyclohexyl turn to a mixture of cyclohexanol/cyclohexanone using a variety of reactions, such as hydrogenation or decomposition.

The decomposition of organic hydroperoxides and, in particular, gidroperekisi of cyclohexyl (GPCG) can be primarily carried out using homogeneous catalysis, i.e., in the presence of a catalyst dissolved in the reaction medium. Thus, in the patent FR-A-1580206 described liquid-phase oxidation of cycloalkane followed by heating the thus obtained solution Gidropark cnym in articles in the Journal of the American Chemical Society (1985), 107 p. 3534-3540 or Journal of Molecular Catalysis (1988), 48, pp. 129-148 described the use of organic salts, such as octanoate cobalt, or complexes dissolved in the liquid organic phase in which the reaction takes place, or in the aqueous phase in contact with this organic phase.

These decomposition gidroperekisi of cyclohexyl may also be carried out by neutralizing present in the environment of acid with alkali metal hydroxide in the presence of metal salts, such as those described in patents US 4720592 and 4238415. However, the output of which is formed of a mixture of cyclohexanol/cyclohexanone is not too high, and the formation of numerous by-products.

In the patent US 3925316 describes how the decomposition of gidroperekisi of cyclohexyl in the presence of homogeneous catalysts consisting of soluble compounds of vanadium, ruthenium or molybdenum. Other catalytic systems based on a pair of different metals in the form of soluble compounds described, for example, in patents US 3401193, 3987100 and 4551553.

The decomposition of hydroperoxides in the presence of homogeneous catalyst is a certain number of difficulties. So, used a significant amount katalysatorrolle, in this connection there is the need to add fresh catalyst. In addition, the presence in the effluent metals, mainly heavy metals, is not very beneficial to the environment, and must, to the extent possible, to avoid it.

In an attempt to resolve the above difficulties it was proposed to carry out the decomposition of hydroperoxides with the use of heterogeneous catalysis, i.e., in the presence of a catalyst which is insoluble in the reaction medium.

In particular, in patent US 4173587 describes the use for the decomposition of the gidroperekisi cumene insoluble compounds of rhenium.

In the patent EP-A-0492807 describes how to obtain phenol and acetone from the gidroperekisi of cominella in the presence of zeolite catalyst type mordenite or faujasite selected from zeolite Y, thermally stable dealuminated zeolite Y, zeolite Y, subject to exchange rare metals, in particular salts of lanthanum, or transition metals, in particular salts of cobalt or Nickel, and Y zeolites treated with fluoride.

In these cases, the metals are also not sufficiently firmly fixed on the carrier, and the use of catalysts is their partial dissolution in reactio is it in action on hydropeaking of cyclohexyl catalyst on a carrier, containing from 2 to 30% (in terms of element) of cobalt oxide deposited on a zeolite carrier or absorbed by this media. This catalyst is not stable in the reaction medium dissolves a significant amount of metal joining. This creates the same problem that was mentioned in relation to homogeneous catalysis.

Earlier in the patent US 2851496 described the use as catalysts for the decomposition of gidroperekisi of cyclohexyl metals of group VIII such as cobalt supported on alumina, silica, carbon or diatomaceous earth. However, this reduced catalyst life.

In the patent EP 659726 describes a method of obtaining a mixture of the alcohol/ketone decomposition of alkylhydroperoxide in the presence of an immobilized on the carrier metal in the presence of the aqueous phase and the main connection. Carrier is a metal oxide such as TiO2or ZrO2, which caused a compound of manganese, iron, cobalt, Nickel or copper.

In the patent US 5298665 describes the use of a catalyst consisting of a metal joints, caused or fixed on the carrier. As metal compounds are named connection with a metal oxide, selected from silica, alumina, titanium oxide. This carrier has on its surface groups are aromatic or aliphatic amines. This catalyst is used to convert alkylhydroperoxide in a mixture of alcohol and ketone.

The above catalysts have a limited lifespan, because in most cases the metal is partially soluble in the medium, due to the fact that the catalysis is mainly dissolved fraction. The amount of catalytically active metal catalyst on the carrier is reduced, and the resulting mixture ketones/alcohols are undesirable impurities in the form of dissolved fraction of the metal.

In patent application WO-A-94/08932 proposed to overcome the aforementioned disadvantages of heterogeneous catalysts by carrying out the decomposition of organic hydroperoxides in the presence of molecular sieves containing oxides of aluminum and/or silicon and/or phosphorus and the metal catalyst is incorporated into the crystal matrix of the molecular sieve. There is reason to believe that the active metal of these heterogeneous catalysts are practically not washed. However, if the problem of leaching of the catalyst into the reaction environment seems so abrahamite reactivation of the catalyst by his Department and calcination. In the framework of the industrial application of this method the need for frequent separation of the catalyst from the reaction medium with a view to its reactivation is highly undesirable.

One of the purposes of the present invention is to overcome these disadvantages by offering a method of obtaining a mixture of alcohols and ketones from alkylhydroperoxide, including heterogeneous catalysis with increased cycle time and service life of the catalyst and to obtain a mixture of the alcohol/ketone, not containing or containing a very small amount of the metal element used as a catalyst.

To this end, the invention proposes a method of obtaining a mixture of alcohols and/or ketones decomposition of alkylhydroperoxide in the presence of a catalyst containing a catalytically active metal element is immobilized on a solid carrier selected from the group comprising the elements belonging to group IB-VIIB or VIII of the Periodic table (CAS version), including the family of lanthanides, characterized in that the metallic element is located on the surface of the mentioned solid carrier in the form of ORGANOMETALLIC fragment of formulas I or II:

the elements, belonging to the group IB-VIIB or VIII of the Periodic table (CAS version), including the family of lanthanides;

R denotes a linear or branched hydrocarbon radical containing from 1 to 12 carbon atoms;

R1 denotes a halogen atom, hydroxyl, alkoxy, carboxyl, amino or an aliphatic, arylaliphatic, aromatic, alkylaromatics hydrocarbon radical which may contain heteroatoms;

X denotes an anion;

n is an integer from 0 to 4;

m is an integer from 1 to 6;

p and q represent integers from 0 to 4.

In a preferred variant of the invention, the metal ion M corresponds to the elements selected from the following preferred groups: chromium, cobalt, copper, iron, manganese, titanium, vanadium, molybdenum, ruthenium, gold, osmium. The preferred elements of the invention are chromium and copper. Suitable for the invention anions are anions that form in the environment preparation of complex soluble salt with the metal M. as an example we can mention the anions of carboxylic acids, such as oxalates and acetates, halides, sulfonates or mixtures thereof.

The media is mainly noroxin zirconium, the oxides of rare earth metals such as cerium oxide, lanthanum oxide, or inorganic compounds, such as lanthanum phosphate. The media can also be selected from zeolites, molecular sieves, such as MSM, HMS or carriers synthesized from polymers containing functional groups, such as polystyrenes, polyacrylonitrile. In the more General case, the invention may be suitable any solid porous structure.

As relevant to the invention catalysts can, in particular, to call the catalysts described in the article by J. H. Clark et al. Catalytic oxidation of alkyi aromatic using a novel silica-supported Schiff base complex, published in J. Chem. Commun. 1998, pp. 1941-1950.

These catalysts are mainly in solution, where a pre-prepared set of metal is fixed in the final stage of the synthesis on the surface of the carrier, more specifically silica. This synthesis method has in particular the advantage that the complex of the metal formed more simply: by applying a suitable solvent.

The media is then added to the environment in which was formed the complex, so that it could gain a foothold in the media.

As an example, the complex is

In these formulas, m, p and q have the above values.

The catalyst prepared in this way has a higher catalytic activity than the catalysts formed by the fixation of the ligand on the media with the subsequent formation of the complex by adding (in the last stage) of metal ions.

Another option for preparation of the catalyst in accordance with the invention consists in adding to the liquid medium of the precursor gel solid media and compounds necessary for the formation of the above-described complex of the metal. Wednesday after this modify in such a way as to cause the formation of a gel, for example, by changing the pH or by adding a co-solvent. This modification of the environment can be achieved by adding one of the compounds necessary for the formation of the complex.

These methods of synthesis described in the above article and are given only as examples and illustrations.

As an example, synthesized thus the catalyst can be called a catalyst, ORGANOMETALLIC fragment which has the following formula IV:

The catalysts used in the method of decomposition of alkylamide the th higher activity and selectivity, observed in the case of homogeneous chromium catalyst.

Along with this, the service life of the catalyst is large, because it has not been shown the phenomenon of deactivation.

Finally, the amount of metal, washed out in the course of the decomposition reaction, is very small, which makes it possible, on the one hand, to lower the amount of the metal used and, on the other hand, to limit the presence of contaminating metal in the resulting mixture of the ketone/alcohol or waste in the process.

The invention is applicable in particular to the decomposition of alkylhydroperoxide obtained by air oxidation of alkanes containing from 3 to 30 carbon atoms.

This reaction is usually conducted in a solvent environment.

Oxidation of alkanes is carried out in classical terms, is widely described in the literature. As an illustration: this oxidation can be carried out in the liquid phase in the presence of pure oxygen, air or oxygen-enriched mixture at a temperature in the range from 80 to S.

Usually in the oxidation of alkanes degree of conversion of the latter is approximately in the range from 1 to 50 wt.%.

This oxidation can be carried out in the absence of catalyst or catalyst Oka.

The resulting alkylhydroperoxide usually soluble in the corresponding alkane, which is used as a solvent. However, there may be used other solvents, such as alcohols, ketones and, in particular, alcohols and ketones produced in the decomposition reaction of gidroperekisi.

The reaction of the decomposition of alkylhydroperoxide spend after that, in the presence of the above catalyst on the carrier. This catalyst is used in the form of a fixed or fluidized bed or in suspension in the medium. The decomposition can be carried out directly formed after the oxidation environment, after washing this reaction medium with water or after extraction of gidroperekisi.

The temperature of the decomposition reaction support between 25 and 200C, mostly in the range of about 70 to 150C., for example at a temperature of the alkane distillation or solvent boiling under reflux.

The number of recovered catalyst depends on the method of carrying out the invention. So, in the case of the fixed layer, the amount of catalyst is more than the amount that is used in the case of the catalyst in suspension.

The concentration of gidroperekisi also moratoria can be separated and optionally isolated from the reaction medium by distillation.

The reaction medium may also be subjected to a new oxidation, for example with nitric acid, with the aim of producing adipic acid.

This reaction medium can also be used as a starting material for the synthesis of caprolactam.

Alkanes that can be used for oxidation, are, in particular, a normal or branched alkanes and cycloalkanes containing from 3 to 30 carbon atoms.

As examples, propane, cyclohexane, Cycloheptane, methylbenzol, ethylbenzene, phenylcyclohexane, difenilmetana, phenylcyclohexane, cyclododecane, 1,2-dicyclohexylmethane, cumene, isobutane, 2-methylpropane, 2-propylbenzoyl, cyclohexene, 4-tert-butyl-1-cycloheptylmethyl, 2-isopropylnaphthalene, fluoren and 1.8-dimethylfuran.

The method is particularly well applicable in the case of oxidation of cyclohexane and decay gidroperekisi of cyclohexyl up of a mixture of cyclohexanone/cyclohexanol.

He is also applicable to the decomposition of alkylhydroperoxide received to others in ways different from the oxidation of alkanes.

The invention will be more fully illustrated using the examples given below solely with the study.

These catalysts include chromium complex, forming the ORGANOMETALLIC fragment, mounted on a silica carrier.

Example 1: Preparation of the catalyst AND

The ethanol containing 3-aminopropyl(trimetoksi)silane, add salicylic aldehyde. The solution immediately becomes yellow. Added to a solution of chromium acetate and stirred the mixture for 30 min prior to the formation of a complex of the following formula:

The mixture is stirred over night, adding industrial silica, sold under the name KIESELGEL 100.

The final product produce by filtration, followed by washing with water and alcohol.

The product is dried for 2 hours at 70C.

The resulting catalyst with a particle size of from 30 to 140 microns has an average pore diameter of 100 .

Molar concentration of chromium is 0,106 mmol per 1 g of catalyst (or 0.57 wt.%).

Example 2: Preparation of catalyst

Example 1 is repeated, using as the carrier instead of the silica KIESELGEL srednepolny silica HMS.

Srednepolny silica HMS receive the following way.

To a mixture of water/ethanol (11,8 mol of water and 3.6 mol of ethanol) is added 0,054 m is filtrowa after aging for 18 h, dried and calcined at a temperature of 600C for 4 hours to remove organic compounds. Can be used and other amines, such as decylamine.

The resulting catalyst contains 0.36 mmol of chromium per 1 g of catalyst (1,80 wt.%).

Example 3: Preparation of the catalyst method Sol-gel

To pure ethanol is added 0.02 mole of salicylic aldehyde and 0.02 mol aminopropyl(trimetoksi)silane. The solution is stirred for 30 min by adding 10 mmol of chromium acetate. Prepare another solution, adding to 100 ml of water 0,049 mol of dodecylamine. To this solution is gradually added ethanol to dissolve dodecylamine.

Both of the thus prepared solution are mixed, immediately adding tetraethoxysilane (0,255 mol). The resulting solution is stirred over night.

The resulting solid green filtered and washed with water and ethanol. The thus obtained solid substance is treated with ethanol and then dried at 70C., removing the solvent.

The resulting catalyst contains 0,073 mmol SG 1 g of catalyst (0,52 wt.%).

Example 4: Decomposition of gidroperekisi of cyclohexyl (GPCG)

The purpose is of cyclohexyl, of 1.36 wt.% cyclohexanone and of 1.37 wt.% cyclohexanol.

40 g of this solution is heated at 80 C, fending off the water azeotrope in the presence of 1 g of the catalyst.

The nature of the added catalyst and duration of the reaction are listed in table 1 together with the degree of conversion and outputs of different chemical compounds.

Different concentrations of cyclohexanone, cyclohexanol and GPCG determined by the following methods:

- Quantitative determination of gidroperekisi of cyclohexyl: the Principle consists in the oxidation of potassium iodide by hydropredict and inverse quantification of the formed iodine with sodium thiosulfate solution.

- The determination of concentrations of ketone and alcohol: Determination is carried out by chromatographic method after recovery contained in the alcohol gidroperekisi reaction with triphenylphosphine.

Chromatographic analysis gives the total concentration of the ketone and total concentration of alcohols.

The concentration of ketones formed and the concentration of the formed alcohols expect given the initial concentrations of ketone, alcohol and residual concentration of gidroperekisi.

Table 1:

- Rt(ol) denotes the output on alcohol compounds (expressed as the number of alcohol per cyclohexanol formed by decomposition GPCG, in relation to theoretical amount of education cyclohexanol, calculated based on the actual number of converted GPCG);

he/ol denotes the molar ratio of ketone to alcohol.

In order to compare experiment was carried out with a homogeneous catalyst based on chromium (di-tert-buildroot) with respect GPCG/IG equal 6550. The degree of conversion (IC) 94% was achieved after 90 min at high selectivity to cyclohexanone (Rt(it)=81,6%, Rt(ol)=26.6 per cent and the ratio of he/ar=3,1).

Held at the same time the analysis of chromium, washed in the reaction environment, shows that in examples 4-6 (catalysts a, b and C according to the invention) chromium concentration is very low (less than 1 part per million).

Example 7:

Used in example 4, the catalyst And Recuperat after 70 min of reaction. Was another one experience in the decomposition hydrop the congestion. Data for this reaction are given in table 2:

Along with this, in the above example 4, the concentration of the washed chromium is of the order of 0.7 mg per 1 kg of the solution, i.e., was washed 0,47% chromium taken. Example 7 this concentration below 0.1 mg/kg of solution, i.e., the number of washed chromium is less than 0.07 per cent.

1. The method of obtaining 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, characterized in that 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, sootvetstvujushij elements belonging to group IB-VIIB or VIII of the Periodic table (CAS version), including the lanthanides;

R denotes a linear or branched hydrocarbon radical containing 1-12 carbon atoms;

R1denotes a halogen atom, hydroxyl, alkoxy, carboxyl, amino or an aliphatic, arylaliphatic, aromatic, alkylaromatics hydrocarbon radical which may contain heteroatoms;

q denotes an integer from 1 to 4;

X represents the anion.

2. The method according to p. 1, characterized in that the metal element M chosen from the group consisting of chromium, cobalt, iron, manganese, titanium, copper, vanadium, molybdenum, ruthenium, gold, osmium.

3. The method according to p. 1, wherein the solid carrier is an inorganic oxide selected from the group consisting of alumina, silica, zirconium oxide, oxides of rare earth metals, titanium oxide or inorganic compounds, such as lanthanum phosphate or zeolites, molecular sieves or media, synthesized from polymers containing functional group.

4. The method according to one of the preceding paragraphs, characterized in that the use of the catalyst obtained by the interaction of a suitable metal salt of salicylic aldehyde and 3-aminopropyl(trimetoksi)silane in a solvent to obtain a complex of the metal of General formula III or IIIa p. 1, which is injected for his vaccinations on the carrier in contact with a solid carrier which can be prepared in situ in the solution in the form of a gel.

5. The method according to one of the preceding paragraphs, characterized in that cycloalkylcarbonyl is produced by oxidation of cycloalkane 6. The method according to one of the preceding paragraphs, characterized in that it includes a step for the gidroperekisi of cyclohexyl oxidation of cyclohexane and decomposition gidroperekisi to cyclohexanone and/or cyclohexanol.

 

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