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

 

(57) Abstract:

The invention relates to a method of obtaining a mixture containing cyclic saturated alkane and the corresponding alkanol. The inventive product is a mixture containing cyclic saturated alkane and the corresponding alkanol. Reagent 1: alkylhydroperoxide in the solvent which is in a mixture, is subjected to decomposition. Reaction conditions: in the presence of metal joints, immobilized on a carrier representing

,

where R1- C2-C6alkyl; R is lower alkoxy; R2-H; R4-NH2where R4- C2-C3alkyl, Y is-S-, -NR3, R3H, n = 0, 1, 2, m = 0, 1, 2, n + m = 2. As use metal complex or salt of cobalt, chromium or iron or a mixture which is soluble in the dispersant. table 2.

The invention relates to a method of producing alkanol and/or alkanol by oxidation of an alkane of 3 to 30 carbon atoms, with oxygen, to obtain gidroperekisi of alkyl, with the subsequent decomposition of the received gidroperekisi of alkyl in the presence of a metallic compound, fixed media, in particular to a method of producing alkenone and/or alkanol, kasasa Gidropress the alkyl mixture in a solvent in the presence of a metallic compound, fixed on the media.

There is a method in which Gidropress cyclohexane obtained by air oxidation, can be converted in high yield to the corresponding ketone or ketone, and alcohol (or alkanol, a) (see European patent A-367326). In the literature often focuses on the oxidation of alkanes, such as cycloalkanes, in particular cyclohexane, to obtain the corresponding alkanol and/or Alcanena. In this way it is possible to distinguish two stages: first, the conversion of alkane to the mixture, containing almost corresponding Gidropress of alkyl, with subsequent transformation (decomposition) of this gidroperekisi of alkyl in the mixture To/A. in Addition to direct transformation of gidroperekisi of alkyl, Gidropress of alkyl during this second stage also often reacts with a significant number of the remaining alkane, which again leads to the formation of K and A. In some cases, this so-called participation alkane plays a significant role in the overall transformation of the alkane and the output mixture To/And that accompanies it.

The main difference between phase oxidation and phase decomposition is that the latter is carried out at lower temperatures. The difference is usually sostavlyali oxidation, largely carried out without a catalyst, a relatively high temperature is used to maintain an acceptable rate of reaction; this produces relatively few side products. Stage of decomposition, which use a significant amount of catalyst that would, in the case of reaction at too high temperature, lead to the production of large quantities of undesirable by-products.

Many catalytic systems have been proposed for use in the above process. In particular, it is known homogeneous catalytic reduction of hydroperoxides of alkyl (see Patent UK And 1212824).

Homogeneous catalysis for the decomposition of hydroperoxides of alkyl is still used for commercial purposes, although education is quite significant waste stream with the catalyst. To avoid these waste streams was proposed to absorb the catalyst on the carrier (see U.S. Patent A-2851496). The activity of such a catalyst, as it turned out, steadily deteriorated. Also known by the system (see EP-A-367326) does not create a stable catalyst active for a long time. Known cobalt-porphyrin complex compounds (see EP-A-MoA provides a method of decomposition of hydroperoxides of alkyl in the application of the catalyst, which retains its activity over a long period of time.

The invention relates to a method for alkane and/or alkanolamide mixture in the solvent by decomposition of gidroperekisi of alkyl, present in mixtures containing Gidropress of alkyl in the solvent, in the presence of a metal compound immobilized on the carrier, the method characterized by the fact that the media contains a group of aliphatic or aromatic amine or a sulfide group.

The carrier preferably has a group with the following structure:

< / BR>
where the substrate is a silica;

n 0, 1, 2, and m is 0, 1, 2, and n + m=2;

R is lower alkoxy;

R1(C2-C6)alkyl;

Y S, -NR3where R3H;

R2-H, -R4-N-H2where R4- (C2-C3)alkyl,

and R1may contain groups of simple ether, and R2, R3, R4may optionally contain 1 or 2 groups of simple ether, alcohol or carboxyl groups.

Used carrier bearing aliphatic or aromatic amino group or a sulfide group, preferably represents a carrier bearing group of the formula R

As X use silicon, but you can also use Ti or Zr. Preference is given to using silicon.

R represents lower alkoxy and may be also ethoxy, methyl, ethyl, isopropoxy, n-propoxy, propyl or butoxy.

R1is a (C2-C6)alkyl, in particular ethyl or propyl, however, R1you can choose from the group of: isopropyl, n-butyl, 1 - or 2-methylpropyl, pentyl, cyclopentyl, n-hexyl, 2-methylpentyl, cyclohexyl, octyl, benzyl, phenyl or 2,2-diphenylpropyl, R1can additionally contain inert heterogroup, such as the atoms of the ether oxygen.

As Y is very suitable sulfur or nitrogen. Sulfide or amine may be primary, secondary or (Amin) and tertiary as long as the valence remains a need for coordination with the metal of the GRU is from each other, in particular methyl, ethyl, propyl,-propyl, butyl, 2-methylpropyl, tert-butyl, hexyl, octyl, or, in particular, 2-amino-ethyl, 2-sulphatoethyl or 3-aminopropyl. Preferably R2means (and, as can happen, R3) H; R4NH2where R4represents C2-3alkyl.

Used media containing an amino group or a sulfide group, may also represent a weak basic ion exchanger, such as, in particular, polystyrene (cross-linked with divinyl benzene), supporting group-NR2, (where R is H, methyl or ethyl), or resin bearing one group S-R.

Complex metal compound or metal salt, which are used, are preferably compound or salt of the metal of the fourth period of groups IB, IVB, VB, VIB or VIII of the periodic system. Examples of suitable metals are cobalt, chromium, vanadium, molybdenum, ruthenium, manganese, titanium and iron are particularly preferred cobalt, chromium and iron. Therefore, preferably used a metal compound includes a compound or salt of the metal of this group. Of course, mixtures of metals may also be used (in relation to the periodic system makes the ACLs "version of CAS."

This catalyst per se known and is used, for example, for the oxidation of cyclohexane (see J. Org. Chem. Vol. 56. 1991, S. 1981 1983). However, the oxidation reaction is essentially different from the decomposition reaction of gidroperekisi of alkyl. In addition, the use of the catalyst in this invention is very advantageous considering the fact that the catalyst is unexpectedly more stable than heterogeneous catalysts of the prior art.

The catalyst can be obtained by impregnation of the carrier, which contains aliphatic amine or sulfide group, with a metal compound, and this metal connection at least a portion of the ligands has a weaker bond with the metal, amine or sulfide group. Then the metal ion forms a complex compound with amine and/or sulfide of a group of media, resulting in receive unexpectedly stable catalyst. It happens unexpectedly, so as, in particular, the complex compound porphyrin cobalt on the media not confirmed its stability for a long time. The metal compound is preferably a metal salt or metal complex compound, restorasi aliphatic or aromatic amine or sulfide group, available on the market or it can be obtained by dispersion of a substrate, such as, for example, silica or alumina-zeolite in an organic liquid, such as, for example, methanol, ethanol, tetrahydrofuran, dioxane, DMSO, toluene, cyclohexanol or acetone. Then, this dispersion may be added organofunctional silane or titanate. Used silane may, in particular, represent a 3-aminopropyltrimethoxysilane, N-methyl-3-amino-propyltrimethoxysilane, 3-aminopropyl(2-methoxypropyl-ethoxysilane, N-amino ethyl-3-aminopropyltrimethoxysilane, N-amino-ethyl-3-aminopropylsilyl-dimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercapto-propeller-dimethoxysilane, para-amino-phenyl-triethoxysilane. Used titanate may, in particular, to represent polkacide(m-AMINOPHENYL)titanate.

Silicone connection or titanate usually enter into the reaction with the substrate for 10 to 300 minutes at a temperature of 0 150oC. Optimal conditions can be easily selected by a person skilled in the art. The product can then be filtered, washed and, if necessary, dried. The product can also be subjected to dalineishimi amino groups or sulfide groups add metal connection. To this end, the carrier preferably is dispersed in the substance, which is soluble metal compound. The mixture is preferably stirred. Also very good, this process can be carried out in a fixed bed. The transformation in the complex compound of the metal with media containing amine or sulfide group usually takes 10 to 300 rpm and is in the range of 0 - 100oC, preferably 20 to 50oC, however, the time and temperature are not critical and may be for practical reasons, chosen in relation to the, without any distinction.

Gidropress of alkyl containing the mixture in a solvent, preferably obtained by oxidation of an alkane of 3 to 30 carbon atoms with oxygen.

In the method according to the invention, the alkane oxidation is carried out in the liquid phase are known in this area follows, using, in particular, air, pure oxygen or mixtures of oxygen and inert gas at a temperature of 120 200oC, in particular 140 180oC, during, for example, 0.1 to 24 hours, preferably 0.5 to 24 hours In this way, in particular, is converted 1 50 alkane, this number can also be within 1 25 Pressure in this process is the Oxidation of the alkane is preferably carried out in the absence of substances, promotes the decomposition of the formed gidroperekisi of alkyl, therefore, for this reaction, the preferred application of the reactor with an inert inner wall, in particular the inner wall of passivated steel, aluminum, glass, enamels and similar materials. If you still require the use of oxidation catalyst, the amount of the transition metal should preferably be very small, in particular about 1 to 10 wt. hours in a million. As the oxidation catalyst can be used compounds, in particular, cobalt, chromium, manganese, iron, Nickel, copper or mixtures thereof. Also suitable fixed ORGANOMETALLIC complex compounds described in this specification.

To decomposition of gidroperekisi in the oxidation mixture, this oxidation mixture may optionally be treated with water or an aqueous solution of alkali metal hydroxide or carbonate of an alkali metal removal and/or neutralization of acids formed during the oxidation, in particular, to pH of the aqueous phase 8 13.

It is possible that the mixture containing Gidropress of alkyl, could concentrate by evaporating a certain amount or just alkane and possibly alkane may be replaced by another RA who were alkane. Furthermore, the mixture can contain a number of alkanol and Alcanena.

Decomposition of gidroperekisi the alkyl mixture in the oxidation is carried out using a fixed metal complex compounds according to the invention. The catalyst decomposition can be used in several ways. As it is recorded on the carrier, can be used as reactors for the suspension and, in particular, reactors with reinforced layer in order to transform the gidroperekisi of alkyl. The heat of reaction released during the decomposition, must be properly apprehended and taken to ensure proper temperature control of the process. This can be very effectively done with the use of reactors for suspensions. In the decomposition process required temperature can then be maintained, in particular by counterflow cooling at least part of the subject heat removal. In this case, will not be required recycling the evaporated product that has a slightly beneficial effect on the yield of the desired product. In this position, the number of identified complex compounds, which must be applied is, in particular, 5 to 250 hours on predpochtitelno use less than 150 hours in a million.

This method can also advantageously be used in the reactor with a fixed bed, as it achieved a relatively high concentration of catalyst, which is particularly beneficial when using a mixture of gidroperekisi with a relatively low concentration.

The temperature for decomposition is usually in the range of 25 - 200oC, preferably a temperature at least 20oC lower than the temperature applied at the stage of oxidation, more specifically a temperature of at least 40oC below. Decomposition of the selected pressure is usually slightly lower than the oxidation. The decomposition is preferably carried out in the presence of oxygen. This improves the yield of the mixture K/A.

Depending on the concentration of the transition metal on the carrier, the concentration of gidroperekisi and temperature decomposition usually takes 5 to 300 minutes, Preferably the residence time of the reaction mixture in the reactor decay is 15 to 120 min, but it's not critical. Using a simple analysis specialist in this field can determine whether any of gidroperekisi in the treated mixture.

The reaction mixture obtained by the decomposition of gidroperekisi, represents and is. In addition, there will be some side products. The mixture may optionally be processed by applying a distillation process in relation to the organic phase, after washing with water, if desired, when removing alkane, which must be returned to the cycle. After this can be carried out distillation desirable products, alkanol and Alcanena. Usually alkanol and alkane should be obtained separately.

Used C3-30alkane may, for example, to represent propane, 2-methylpropane, Cycloheptane, cyclohexane, methylbenzol, ethylbenzene, 2-propylbenzoyl, phenylcyclohexane, cyclohexen, difenilmetana, vinylcyclohexane, 4-tertbutyl-1-cycloheptylmethyl, 2-isopropylnaphthalene, fluoren, 1,8-dimethylfuran, 1,2-dicyclohexylmethane. Alkane may contain aromatic groups and Ethylenediamine group. Alkane may be branched, linear and/or cyclic.

This method is especially suitable for oxidation of cycloalkanes with 4 to 18 carbon atoms, in particular for the oxidation of cyclohexane, cyclooctane and cyclododecane, the products of the oxidation reaction of cyclohexane is particularly suitable for use in obtaining or caprolactam (nylon-6), or adipine what canola and cyclohexane, as it turned out, clean enough without additional processing to further transformation into caprolactam.

The synthesis.

Example I. To 100 g of silica (Grace, SG524, surface area BET of 540 m2/g, particle size 1 to 3 mm) was added 500 ml of methanol at room temperature. This suspension was stirred for 15 minutes then added 250 g of 3-aminopropyltrimethoxysilane. The suspension was stirred at room temperature for 1 h After filtration, the solid was washed in 200 ml of toluene. This washing was repeated twice. Then the product was dried. The carbon content in the resulting modified so the silica (type a) is 63 g/kg

When the modification of silica with different surface area BET the number of aminosilane regulated directly proportional to the surface area of the silica, in particular in respect of silica with a surface area BET of 390 m2/g used 180 g of silane. The reaction time and temperature remained the same. It turned out that other solvents, such as, for example, ethanol and toluene, have no significant impact on the result. When using silica with different particle size distributions the results of an eye the tx2">

Example II. To 100 g of silica (Grace 1000MP, surface area BET 50 m2/g, a particle size of 1 to 3 mm) was added 500 ml of methanol at room temperature. This suspension was stirred for 15 minutes then added 25 g of N-2-amino-ethyl-3-aminopropyl-trimethoxysilane. The suspension was stirred at room temperature for 1 h After filtration, the solid was washed in 200 ml of toluene. This washing was repeated twice. Then the product was dried. The carbon content of the thus obtained modified silica (type B) was 8 g/kg

Example III. To 50 g of silica (Grace SG254 surface area BET of 500 m2/g, the particle size of 0.8 to 1.4 mm) at room temperature was added 250 ml of methanol. This suspension was stirred for 15 minutes then added 25 g of 3-mercaptopropionylglycine. The suspension was stirred at room temperature for 1 h After filtration, the solid is washed with 200 ml of methanol. This washing was repeated twice. The product is then dried. The sulfur content in the thus obtained modified silica (type C) was 32 g/kg

Example IV. To 50 g of silica (Grace, SG254, surface area BET of 540 m2/g, the particle size of 0.8 to 1.4 mm), with whom the 25 g of para-AMINOPHENYL-biotoxicity. The suspension was stirred at room temperature for 1 h After filtration, the solid was washed in 200 ml of ethanol. This washing was repeated twice. The product is then dried. The nitrogen content in the thus obtained modified silica (type D) was 28 g/kg

You can usually say that if you are silanes having the General formula R1-Si(OR2)3where R2denotes a methyl group or ethyl group, the above procedure can be used for surface modification of silica.

Example V To 10 g of type a was added 165 ml of a solution of Co(II)-acetotartrate in water (100 g/l). The suspension was stirred for 3 hours at a temperature of 47oC. After filtration, the solid is washed with 400 ml of water. The washing procedure was repeated twice. After drying the resulting silica (type a-Co-I) contained 33 g Co/kg

When you change, in particular, reaction time and temperature was found that on the basis of silica type And could be obtained a catalyst having a content of cobalt in the range from 1 to 8 In table. 1 shows some of these results.

Example VI. To 10 g type was added 165 ml of a solution of Co(II)-acetotartrate in water (100 g/l). Susp ml of water. The washing procedure was repeated twice. After drying the thus obtained silica (B-Co-I) contained 3 g Co/kg

Example VII. To 10 g of type C was added 200 ml of a solution of Co(II)-acetotartrate in water (100 g/l). The suspension was stirred at room temperature for 5 hours After filtration, the solid is washed with 400 ml of water. The washing procedure was repeated twice. After drying the thus obtained silica (type C Co-I) contained 13 g Co/kg

Example VIII. To 10 g of type D was added 165 ml of a solution of Co(II)-acetotartrate in water (100 g/l). The suspension was stirred for 4 hours at a temperature of 47oC. After filtration, the solid is washed with 400 ml of water. The washing procedure was repeated twice. After drying the resulting silica (type D-Co-I) contained 45 g Co/kg

Example IX. To 15 g of type a was added to 100 ml of a solution of Cr(NO)39 H2O in water (33 g/l). The suspension was stirred at room temperature for 18 hours After filtration, the solid is washed with 400 ml of water. The washing procedure was repeated twice. After drying the thus obtained silica (type C-Cr-I) contained 14 g Cr/kg

Example X. To 15 g of type a was added to 100 ml of a solution of Fe(II)-sulfatreat in water (12 mawali in 400 ml of water. The washing procedure was repeated twice. After drying, the thus obtained silica (type a-Fe-I) contain 29 g Fe/kg

Example XI. To 15 g of type a was added to 100 ml of a solution of Cr(NO)39H2O (33 g/l) and CoSO4(23 g/l) in water. The suspension was stirred at room temperature for 18 hours After filtration, the solid is washed with 400 ml of water. The washing procedure was repeated twice. After drying, the thus obtained silica (type A-Co-Cr-I) contained 13 g Cr/kg and 12 g Co/kg

Periodic experiments.

Example XII. To 50 g of a mixture of oxidation of cyclohexane containing 200 mmol cyclohexyl-gidroperekisi (CGGP), 60 mmol of cyclohexanol (OL) and 30 mmol of cyclohexanone (ON) per kilogram, was added 0.5 g A-Co-I at a temperature of 75oC. This mixture was stirred at the same temperature until complete decomposition CGTP. For the decomposition was monitored using iodometric titration. Constant speed of reaction of the first order was equal to 2.8 10-3kg rest. (min g cat). Selectivity based on OL + ON formed in relation to developed CGTP was 112 Attitude OL/ON was 1.6. The catalyst could be used many times without any decrease of activity.

Comparative is per million of Co in solution). The value of K was 2.0 10-2min-1during the first 20 min of decomposition. After 20 min, the catalyst showed a strong decrease of activity. The selectivity to OL + ON was 91.6 Attitude OL/ON was 2.2. Reuse was impossible.

Examples XIII-XXV.

Example XII was repeated with other catalysts. The results are shown in table. 2.

Comparative experiment B.

Repeating the example XXIV, when this catalyst was Fe(II) sulfate heptahydrate (70 hours per million relative to the fluid). Due to the fact that the catalyst with Fe was not dissolved in the oxidation product, the rate of decomposition could be considered as zero.

Comparative experiment C.

Example XXIII was repeated, with the catalyst consisted of Cr-2-ethylhexanoate (70 hours per million in solution). The value of K was 0,008 min-1. The selectivity to OL + ON was $ 91.7 Attitude OL/ON was 0.2. The catalyst could be reused.

Example XXVI. Example XII was repeated, but now also allow air through the reaction mixture. This led to an increase in yield up to 114 Attitude OL/ON fell to 1.3.

Example XXVII. To 50 g of a mixture of oxidation of cyclododecane, soderjaschim, 0.5 g) was added A-Co-5 at a temperature of 75oC. This mixture was stirred at the same temperature until complete decomposition CDGP. For the decomposition was monitored using iodometric titration. Constant speed of reaction of the first order was 2.94 10-3kg rest./min g cat. Selectivity based on DOL + DON, educated in relation to developed CDGP was 108 Attitude DOL/DON amounted to 1.4. The catalyst could be used many times without any significant decrease in activity.

Continuous experiments.

Example XXVIII. In a column of diameter 3 cm and a length of 10 cm was administered to 29 g A-Co-8. Through this column at a rate of 20 g/h was used in the oxidation product referred to in example XII. The temperature in the column was maintained at 75oC. Thus reached the turning more than 80 Catalyst was tested for over 1000 hours and then he showed no reduction in activity; in addition, the analysis of organic effluent showed that the concentration of Co in this effluent was less than 2 h per billion. Selectivity on OL + ON was more than 100

Comparative experiment.

To 10 g of silica (Grace SG254, surface area BET of 540 m2/g, a particle size of 1 to 3 mm) was added 165 mm repole filtration, the solid is washed with 400 ml of water. The washing procedure was repeated twice. After drying the resulting silica contained 92 g Co/kg In a column of diameter 3 cm and a length of 10 cm was injected 7 g of this catalyst. Through this column at a speed of 40 g/h was used in the oxidation product referred to in example XII. The temperature in the column was maintained at a level of 80oC. the first time the transformation was achieved thus a value of more than 80 Catalyst, however, was clearly lost activity, resulting after 1000 h of his activity fell to becoming less than 20 Selectivity on OL + ON was 89%

Comparative experiment e

On the silica type a (Grace SG239, surface area BET of 390 m2/g, a particle size of 1 to 3 mm) was associated Co-Tetra-sulfochloride-phthalocyanine (see, in particular, EP-367326). The Co content in the thus obtained catalyst was 5 g/kg In a column of diameter 3 cm and a length of 10 cm were introduced 10 g of this catalyst. Through this column at a rate of 20 g/h missed the oxidation product referred to in example XII. The temperature in the column was maintained at 75oC. the first time the transformation was achieved thus more than 90 Turning quickly fell to 20 then remaining stable (the duration of the experience more than 500 hours).

Example XXIX. Example X is Yunosti after 1000 hours

The method of obtaining a mixture containing cyclic saturated alkane and the corresponding alkanol in the solvent, decomposition of alkylhydroperoxide, which is present in a mixture containing alkylhydroperoxide in a solvent, in the presence of metal joints, immobilized on a carrier, wherein the carrier is a compound with the following structural formula:

< / BR>
where the substrate is silica,

R is lower alkoxy,

R1(C2-C6)alkyl,

R2-N,-R4-NH2where R4- (C2-C3)alkyl,

Y-S-, -NR3where R3-H,

n 0,1,2, m 0,1,2, and n + m 2,

as metal joints use a complex or salt of cobalt, chromium or iron or a mixture which is soluble in the dispersant used for dispersing media.

 

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7 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: one of method versions is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification and possibly partial recycling into reaction zone(s) of one or several components of reaction mixture. Decomposition is carried out in presence of inert easily-boiling solvent, which contains mainly hydrocarbons, whose boiling temperature is lower than 70°C, preferably lower than 40°C, but not lower than minus 1°C, which is partially evaporated directly from reaction zone(s) and partially distilled from obtained reaction mixture, is in liquid state returned to reaction zone(s) with supporting in it (them) temperature from 1 to 70°C, preferably from 10 to 45°C. Second method version is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification. Applied is easily-boiling solvent, which after separation from reaction mixture, possibly with part of ketone, is recycled into reaction zone(s), and sulfocationite catalyst in H+ form, resistant in liquid media, containing alkylaromatic hydroperoxides, ketones, phenol and hydrocarbons in large amount, at temperatures up to 70°C, in fine-grain or coarse-grain form, possibly, in form of mass-exchange filling with size from 1.5 to 25 mm.

EFFECT: obtaining phenol and ketones without formation of large amount of by-products and resins and practically without equipment corrosion.

14 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to production of phenol, method of extracting phenol from products of splitting cumene hydroperoxide and to a device for extracting phenol from products of splitting cumene. The method of producing phenol involves the following stages: i) oxidation of cumene, obtaining a reaction mixture containing cumene hydroperoxide and unreacted cumene; ii) splitting products obtained from stage i), obtaining a mixture of splitting products containing at least phenol, acetone, hydroxyacetone, unreacted cumene and water; iii) treatment of the mixture of splitting products obtained on stage ii) through distillation, which involves separation of the mixture of splitting products into at least three fractions using a single fractional distillation stage through: putting the mixture of splitting products into a distillation column, removal of the first fraction, containing acetone, from the upper part of the distillation column, removal of the second fraction, containing phenol, from the lower part of the distillation column, and removal of the third fraction, containing at least unreacted cumene, hydroxyacetone and water, in form of an off-stream. The outlet opening of the off-stream is higher the area for putting in the mixture of splitting products into the distillation column, characterised by removal of heat from the distillation column. The section for removing heat is higher than the outlet opening of the off-stream of the third fraction.

EFFECT: increased energy efficiency of methods using old technology, while maintaining quality standards and total output of end products.

25 cl, 6 dwg, 1 ex

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

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

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to an improved method for synthesis of 2,6-di-(3,3',5,5'-di-tert.-butyl-4,4'-oxybenzyl)-cyclohexane-1-one used as a stabilizing agent of polyolefins and low-unsaturated carbon=chain rubbers. Method involves interaction of cyclohexanone with N,N-dimethyl-(3,5-di-tert.-butyl-4-oxybenzyl)amine in the ratio = (1-1.2):2, respectively, and process is carried out at temperature 125-145°C up to ceasing isolation of dimethylamine. Method provides simplifying technology and preparing the end product with the yield 61-85.4%.

EFFECT: improved method of synthesis.

12 tbl, 23 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 3-bromoadamantyl-1-alkyl(aryl)-ketones of the general formula: , wherein that can be used as intermediate substances for synthesis of some biologically active compounds. Method involves interaction of 1,3-dehydroadamantane with α-bromoketones of the following order: α-bromoacetone, α-bromoacetophenone, α-bromocyclohexanone in the mole ratio of reagents = 1:(2-3), respectively, in absolute diethyl ether medium, at temperature 34-40°C for 3-4 h. Method provides preparing the claimed compounds with high yield.

EFFECT: improved method of synthesis.

3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of continuous oxidation of saturated cyclic hydrocarbons using oxygen, into a mixture of hydroperoxide, alcohol and ketones. The method involves feeding into the lower part of a column and in parallel flow, a stream of oxidisable liquid hydrocarbon and a gas stream containing oxygen, and degassing the liquid phase in the upper part of the column by forming a gas dome and extraction of the degassed liquid phase. The gas containing oxygen is let into different compartments of the column, and into the dome and/or liquid phase at the level of the degassing zone, or directly above. A stream of non-oxidising gas with output sufficient for maintaining concentration of oxygen in the gas layer at the level of volume concentration, less than or equal to the upper limiting concentration of oxygen is supplied.

EFFECT: possibility of implementing a method with high selectivity on an explosion safe level.

9 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing cyclohexanone from cyclohexane, involving the following stages: oxidation of cyclohexane to hydroperoxide of cycohexyl with oxygen in the absence of a catalyst, purification of the reaction medium by washing with water, decomposition of hydroperoxide of cycohexyl to cyclohexanol and cyclohexanone in the presence of a catalyst, extraction of the cyclohexanol/cyclohexanone mixture for separating unreacted cyclohexane and separation of products with boiling point higher than that of the cyclohexanol/cyclohexanone mixture, dehydrogenating cyclohexanol contained in the cyclohexanol/cyclohexanone mixture, in the presence of a dehydrogenation catalyst, distillation of the obtained mixture so as to obtain first run (F1) at the first stage, containing compounds with boiling point lower than that of cyclohexanone, and a last run (Q1) and distillation of the last run (Q1) to obtain a first run (F2) at the second stage, formed from cyclohexanone, and a last run (Q2).

EFFECT: obtaining highly pure cyclohexanone, suitable for use as raw material for synthesis of ε-caprolactam.

6 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves preparation of a reaction mixture at room temperature consisting of the alcohol to be oxidised, sodium bicarbonate, an organic solvent and a nitroxyl radical. Electrolysis is carried out on platinum electrodes with current of 1 A and temperature of 20-25°C. Potassium iodide is added to the reaction mixture. The organic solvent used is dichloromethane and the nitroxyl radical used is 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl of formula: with ratio of alcohol to nitroxyl radical equal to 10:1.

EFFECT: invention ensures high output of end products a within short period of time and less expenses on electricity using a high-technology method.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a mixture of cyclohexanol and cyclohexanone which are intermediate products in production of polyamides nylon-6 and nylon-6.6. The method is realised at high temperature and high pressure and involves the following successive cycles: oxidation of cyclohexane - decomposition of cyclohexylhydroperoxide, wherein oxidation of cyclohexane and decomposition of cyclohexylhydroperoxide are carried out in separate series-connected reactors without intermediate separation of the aqueous phase, whereby in each separate cycle, cyclohexane is oxidised with air or an oxygen-containing gas in liquid phase in the absence of a catalyst until conversion of cyclohexane of not more than 1.5 mol %, and the cyclohexylhydroperoxide formed during oxidation of cyclohexane is decomposed on a heterogeneous catalyst in a separate reactor until conversion of not less than 90 mol %.

EFFECT: method increases overall selectivity of converting cyclohexane to cyclohexanone and cyclohexanol and also considerably reduces formation of by-products.

9 cl, 19 ex, 2 tbl, 1 dwg

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