The method of producing hydroperoxides

 

(57) Abstract:

The invention relates to a method of producing hydroperoxides by oxidation of hydrocarbons oxygen-containing gas in the presence of certain compounds for the selective conversion of hydrocarbons to the corresponding hydroperoxide. These specific compounds are compounds capable of capturing free radicals, and their preferred examples include oxygen-, nitrogen-, phosphorus-, gray-, carbon - and silicon-containing radicals and compounds capable of forming such radicals in the reaction system. This method is applicable to the oxidation of hydrocarbons, including cumin, cimen, m-diisopropylbenzene, p-diisopropylbenzene, 1,3,5-triisopropylbenzene, isopropylnaphthalene, diisopropylnaphthalene, isopropylphenyl and diisopropylphenyl. The technical result - obtaining corresponding hydroperoxides with high selectivity. 11 C.p. f-crystals.

THE TECHNICAL FIELD TO WHICH THE INVENTION RELATES

The invention relates to a method of producing hydroperoxides, which involves the oxidation of a hydrocarbon gas containing oxygen, and the election converting it into the corresponding hydroperoxides.

T is, the absence of a catalyst to obtain the corresponding hydroperoxides known a technology of auto-oxidation. However, to increase the rate of accumulation of hydroperoxides when carrying out this reaction it is necessary to increase the reaction temperature. But by raising the reaction temperature to increase the rate of accumulation there is a thermal decomposition product of the hydroperoxide, which leads to deterioration of selectivity. In other words, because there is such a relationship between growth rate and selectivity, that is, when increasing one decreases the other, it is difficult to maintain both at high levels.

Already, attempts were made to oxidize hydrocarbons in the state of gas containing oxygen using a catalyst to influence the rate and/or selectivity upon receipt of the corresponding hydroperoxides (for example, Japanese patent publication SHO 55-50020).

The creators of the present invention were convinced that there must be a way to ensure high selectivity with overcoming the interdependence between growth rate and selectivity while providing commercially viable accumulation rates. On the oblea, creating the present invention.

In the course of developing the invention, it was found that the oxidation of hydrocarbons oxygen-containing gas in the presence of a compound is effective in converting it into the corresponding hydroperoxides.

In particular, in accordance with the present invention proposes a method of oxidation of a hydrocarbon gas containing oxygen, the corresponding hydroperoxides with high selectivity.

DISCLOSURE OF THE INVENTION

The method of producing hydroperoxides according to the present invention is based on providing the very highest possible selectivity through the use of compounds capable of capturing radicals, as a specific compound in the oxidation of a hydrocarbon gas containing oxygen. The present invention is characterized by the fact that carry out oxidation of hydrocarbons oxygen-containing gas in the presence of the compound that can capture radicals, and electoral converting it into the corresponding hydroperoxides.

THE BEST OPTION OF CARRYING OUT THE INVENTION

The original examples of hydrocarbon include paraffin wax, having a secondary atom in the material include (but are not limited to) isobutene etc. as a paraffin having a secondary carbon atom, Panten, isobutene etc. as olefin, cyclopentane, cyclohexane, etc. as cycloparaffin and cumin, cimen etc. as arylalkyl hydrocarbon.

As an example arylalkyl hydrocarbon, you can specify the connection represented by the following General formula (I):

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(where P and Q which can be the same or different from each other, represent hydrogen or alkyl group, x represents an integer from 1 to 3, and Ar represents an aromatic hydrocarbon group corresponding to the value of x).

In the General formula (I) is preferred when at least one of the symbols of P and Q represents an alkyl group, and particularly preferred, when they both represent alkyl group. In particular, as mentioned alkyl group, preferred is a methyl group.

In addition, as examples of the aromatic hydrocarbon group can be called a hydrocarbon group corresponding to the value x, which can be produced from benzene, naphthalene, diphenyl, simple diphenyl ether and so on, preferably a hydrocarbon group, sootvetstvuushuu preferred examples arylalkyl hydrocarbon include (but are not limited to) diisopropylbenzene, such as cumin, cimen, m-diisopropylbenzene and p-diisopropylbenzene, triisopropylbenzene, such as 1,3,5-triisopropylbenzene, ethylbenzene, second-butylbenzoyl, second-mutilative, isopropylnaphthalene, diisopropylnaphthalene, such as 2,6-diisopropylnaphthalene, isopropylphenyl, diisopropylphenyl, such as 4,4'-diisopropylphenyl, and mixtures of at least two of them. Most preferred is cumin.

The compound of the present invention, which can capture radicals, refers to compounds capable of capturing radicals, and it doesn't matter itself if the connection has this ability, or it acquires this ability under the reaction conditions.

Examples of compounds of the present invention, which can capture radicals include radicals of oxygen, nitrogen, phosphorus, sulfur, carbon and silicon, and compounds which form these radicals in the reaction system.

In the method according to the present invention can be used either radicals stable at room temperature, or compounds which form radicals under the reaction conditions.

During the oxidation of hydrocarbons, oxygen-containing gas are formed of different by-products. In kilcarbery, the acetophenone and dicumylperoxide. It is assumed that in the course of the reaction system are alkyl radicals, such as Cumyl, Kumaritashvili, hydroxyacyl and so on, Apparently, the compound that can capture radicals, in some ways affects these radicals, for example, capturing radicals that cause the reaction, the formation of such by-products, resulting in improved selectivity to hydroperoxide corresponding to the original hydrocarbon.

When choosing the method according to the present invention, the compound that can capture radicals, you can use the difference in energy levels SOMO (single occupied molecular orbit) ((SOMO) between radical compounds (or produced from it), which can capture radicals, and captured by the radicals. Energy level SOMO calculated by the method described below. It is desirable to select a compound that can capture radicals to the difference of the energy levels SOMO ((SOMO) was usually 0-10 eV, preferably 0-4 eV and more preferably 0-1 eV.

For example, it is desirable to select a compound that can capture radicals in the way the current oxidizable hydrocarbon, was as follows:

(SOMO) = |a(SOMO)-b(SOMO)| = 0-10 eV,

where a(SOMO) is SOMO energy level of the compound that can capture radicals, or produced from it radical, a b(SOMO) represents the energy level of the SOMO of the radical corresponding oxidizable hydrocarbon.

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(where P and Q represents hydrogen or alkyl group may be the same or different, x represents an integer from 1 to 3, and ar represents an aromatic hydrocarbon group corresponding to the value of x). Method of calculation (SOMO):

Structural calculation radical perform semiempirical molecular orbits (method MNDO-PM3: MORAS) to calculate (SOMO).

Energy level (SOMO) of pradical determined by structural calculation of the corresponding radical.

At lower (SOMO) is easier to capture a hydrocarbon radical. The difference (SOMO) is in the range of usually 0 to 10 eV, preferably 0-4 eV and more preferably 0-1 eV.

A characteristic feature of the use of compounds having suitable value (SOMO), is that compared with the case where such a connection is not added at the same rate of accumulation of the selectivity of hydrocarbons with high selectivity and high concentration.

As one of the specific examples of the compound that can capture radicals, can be called the oxygen radical and the compound which forms the oxygen radical in the reaction system.

As oxygen radical according to the present invention may be a compound represented by the General formula (II):

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(where Z represents a nitrogen, sulfur or phosphorus, X is any substituted group, and n represents an integer from 1 to 4, satisfying Z), or a compound that forms a compound represented by the General formula (II) in the reaction system.

On the substituting group X in the General formula (II) we can say the following:

substituting group X, which may be the same or different, may represent hydrogen atom, halogen atom, hydrocarbon group, a residue of heterocyclic compounds, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group or a silicon-containing group or a ring formed by at least two specified groups, connected to each other.

As the halogen atom are fluorine atoms, chlorine, bromine and iodine.

To the E. 1-30, preferably 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; an unbranched or branched alkeneamine group having 2-30, preferably 2-20 carbon atoms, such as vinyl, aryl and Isopropenyl; an unbranched or branched alkyline group having 2-30, preferably 2-20 carbon atoms, such as ethinyl and propargyl; cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and substituted; unsaturated cyclic hydrocarbon group having 5-30 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl, and aryl group having 6-30, preferably 6-20 carbon atoms, such as phenyl, benzyl, naphthyl, diphenyl, triphenyl, tenantry and anthracene.

The hydrogen atom in the specified hydrocarbon group may be substituted by a halogen atom. Examples of such hydrocarbon groups include halogen-substituted hydrocarbon group having 1-30, preferably 1-20 carbon atoms, such as trifluoromethyl, pentafluorophenyl and chlorophenyl.

In addition, the above-mentioned PMI above. Examples of such hydrocarbon groups include substituted aryl group, alkyl groups such as benzyl and Cumyl; a substituted alkyl group, aryl groups such as tolyl, isopropylphenyl, tert-butylphenyl, dimetilfenil and di-tert-butylphenyl; and substituted aryl groups in which the aryl group is substituted by alkoxygroup, aryl group or arroceros. In addition, the above-mentioned hydrocarbon groups may contain the following residue of heterocyclic compounds, oxygen-containing group, nitrogen-containing group, a group containing boric acid, sulfur-containing group, phosphorus-containing group or a silicon-containing group.

One of them is particularly preferred hydrocarbon groups are, in particular, unbranched or branched alkyl group having 1-30, preferably 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; aryl groups having 6-30, preferably 6-20 carbon atoms, such as phenyl, naphthyl, diphenyl, triphenyl, tenantry and anthracene; and substituted aryl groups having 1-5 substituents, such as alkyl or alkoxygroup, having 1-30, the different atoms.

Examples of the residue of heterocyclic compounds include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and Piran, the remains of sulfur-containing compounds such as thiophene, and groups with specific residues of heterocyclic compounds, optionally substituted substituting groups such as an alkyl group and alkoxygroup having 1-30, preferably 1-20 carbon atoms.

Examples of oxygen-containing groups include alkoxygroup, alloctype, ester group, acyl group, carboxyl group, a carbonate group, a hydroxy-group, proxygroup and anhydrite group of carboxylic acid.

Examples of the above alkoxygroup include alkoxygroup having 1-30 carbon atoms, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy. Examples of alloctype include alloctype having 6-30 carbon atoms, in particular phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenol. Examples of ester groups include ester group having 1-30 carbon atoms, in particular the atomic charges, benzoyloxy, methoxycarbonyl, Fenech atoms, in particular formyl group, acetyl group, benzoyloxy group, p-chlorobenzoyloxy group and p-methoxybenzoyl group.

Examples of nitrogen-containing groups include amino group, aminogroup, amide group, kidney group, hydratherapy, hydrosonography, a nitrogroup, nitrosolobus, cyano, isocyanurate, ester group, cyanic acid, amidinopropane, datograph and the amino group converted into ammonium salt.

Examples of the above amino group include an amino group having 0 to 30 carbon atoms, in particular dimethylamino, ethylmethylamino, diphenylamino. Examples of aminogroup include aminogroup having 1-30 carbon atoms, in particular methylamino, ethylimino, propylimino, Butylimino, phenylimino. Examples of aminogroup include aminogroup having 1-30 carbon atoms, in particular acetamido, N-methylacetamide and N-methylbenzamide. Examples of aminogroup include aminogroup having 2-30 carbon atoms, in particular acetamido, benzamido.

Examples of boron-containing groups include Brandolino group, Brandolino group and dibenyline group.

Examples of sulfur-containing groups include mercaptopropyl, thioester complex gr the PPU, thiocyanato group, isocyanate group, complex sulfonating group sulfonamidnuyu group, dicarboximido group, dithiocarboxylate group, alphagroup, sulfonyloxy group, sulfinyl group and sulfonyloxy group.

Examples of the above complex thioester groups include thioester group having 1-30 carbon atoms, in particular acetylthio, benzylthio, methylthiouracil and phenylthiocarbamyl. Examples of ancilliary include alkylthiols having 1-30 carbon atoms, in particular methylthio, ethylthio. Examples sulfonamidnuyu groups include sulfonamidnuyu group having 0 to 30 carbon atoms, in particular vinylsulfonate, N-methylsulfonate and N-methyl-p-toluensulfonate. Examples of aristocraty include killigrew having 6-30 carbon atoms, in particular phenylthio, methylphenylthio, naphthylthio. Examples of complex sulfonating groups include complex sulfonating group having 1-30 carbon atoms, in particular the esters of methylsulfonate, ethylsulfonyl and vinylsulfonic acids.

Examples fosforsoderzhashchie groups include was the group, phosphoryl group, thiophosphoryl group and potatorum.

Examples kremniyorganicheskoy siocsiwap, in particular methylsilyl, dimethylsilane, trimethylsilyl, Atisreal, dietildisul, triethylsilyl, diphenylmethylsilane, triphenylsilane, dimethylaniline, dimethyl-tert-Boticelli and dimethyl(pentafluorophenyl)silyl. Of them, preferred are methylsilyl, dimethylsilane, trimethylsilyl, Atisreal, dietildisul, triethylsilyl, dimethylphenylsilane and triphenylsilane. Especially preferred are trimethylsilyl, triethylsilyl, triphenylsilanol and dimethylphenylsilane. Specific examples uglevodorodyonogo siocsiwap include trimethylsiloxy.

Examples of compounds of General formula (II) include (but are not limited to, for example, the following connections:

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As an example nitroxide radical of the compounds of General formula (II) include a compound represented by the General formula (III):

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(where m represents an integer from 0 to 3, D and D' are each separately

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A, B, X1X2, R1, R2, R3, R4and W are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen, and each atom in the P> Substituting group in the General formula (III) may be the same as specified in example substitutional group X in the above General formula (II). Preferred examples of the hydrogen or replacement groups in the General formula (III) are hydrogen, an alkyl group, aryl group, halogen, cyano, amino group, the group isothiocyanato acid, -COORa (where Ra is hydrogen, alkyl group and aryl group), (di)acylaminoalkyl group, hydroxyl group, hydroxyalkyl group, alkoxygroup, arielalexisxrp, -CONRbRc (where Rb and Rc are each separately a hydrogen, alkyl group and aryl group), exogroove (= O) group imide maleic acid, the group of phosphoric acid, the group =NH, or a divalent group.

Examples of the above nitroxide radicals may include a compound having a structure in which two or more structures of the General formula (III) are linked through any of the groups X1X2And, and W.

It is preferred, when all the characters R1, R2, R3and R4in the General formula (III) represent a group selected from alkyl groups. For example, the preferred compounds can be called tetraammineplatinum)sebacate or of 2.2.5.5-tetraalkylfuranidones radical or the specified connection, substituted by the aforementioned group.

Specific examples of the compounds of General formula (III) include, but are not limited to) the following connections:

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(where Me represents methyl group, Et represents ethyl group, and Ph represents a phenyl group (this also applies to the further description of the present invention), and p and q are respectively an integer from 0 to 30).

As connections are becoming nitroxide radical in the reaction conditions, can be called a connection, which turns into nitroxide radical represented by the above General formula (III) under the reaction conditions, or compounds represented by the following General formula (V), (VI) and (VII):

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(where n represents an integer from 0 to 4, and R5and R6are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen-free).

Each of the substituting groups in the General formula (V) may be the same group as mentioned in example substituting group X in the and, arylalkyl group, alkoxygroup or arielalexisxrp and predpochtitelnei example R6can be hydrogen or an alkyl group.

As examples of each of the alternate groups of General formula (V) halogen includes F, Cl, Br and I; an alkyl group preferably includes an alkyl group having 1-10 carbon atoms, such as methyl, ethyl, n-sawn, ISO-propyl, n-bucilina, isobutylene, second-bucilina, tert-bucilina and isoamylene group; arylalkyl group includes comilog group; alkoxygroup preferably includes alkoxygroup having 1-10 carbon atoms, such as methoxy group, ethoxypropan, n-propoxylate, isopropoxy, n-butoxypropyl, isobutoxy, second-butoxypropan and tert-butoxypropan; and arielalexisxrp includes kumelachew.

Specific examples of the compounds of General formula (V) include, but are not limited to, N-hydroxyphthalimide and N-methoxyflavone:

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(where R7, R8and R9are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen-free).

Each of the substituting groups in certain of the above General formula (II). Preferred examples for R7, R8and R9are halogen, an alkyl group or allogeneically group.

As examples of each of the alternate groups of General formula (VI) halogen includes F, CL, Br and I; an alkyl group preferably includes an alkyl group having 1-10 carbon atoms, such as methyl, ethyl, n-sawn, ISO-propyl, n-bucilina, isobutylene, second-bucilina, tert-bucilina and isoamylene group; and halogenation group includes triptorelin group.

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(where 1 is an integer from 0 to 3, and Y, R10and R11are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen-free).

Each of the substituting groups in the General formula (VII) may be the same group as mentioned in example substituting group X in the above General formula (II). Preferred examples of the substituting groups are halogen, an alkyl group, arylalkyl group, alkoxygroup or arielalexisxrp.

Halogen includes F, Cl, Br and I; an alkyl group preferably includes an alkyl group, it is nye, second-bucilina, tert-bucilina and isoamylene group; arylalkyl group includes comilog group; alkoxygroup preferably includes alkoxygroup having 1-30 carbon atoms, such as methoxy group, ethoxypropan, n-propoxylate, isopropoxy, n-butoxypropyl, isobutoxy, second-butoxypropan and tert-butoxypropan; and arielalexisxrp includes kumelachew.

Specific examples of the compound that can capture radicals include nitrogen-containing radical or a compound which forms a nitrogen-containing radical in the reaction system.

Specific examples of the compound that can capture these radicals include (but are not limited to) the following connections:

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Specific examples of the compound that can capture radicals include phosphorus-containing moiety or compound that forms a phosphorus-containing radical in the reaction system.

Specific examples of the compound that can capture these radicals include (but are not limited to) the following connections:

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Specific examples of the compound that can capture radicals include CE is>/P>Specific examples of sulfur-containing radicals include, but are not limited to) the following radicals:

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Specific examples of the compound that can capture radicals include carbon-containing radical or a compound that forms a carbon-containing radical in the reaction system.

Specific examples of carbon-containing radical include, but are not limited to) the following radicals:

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Specific examples of the compound that can capture radicals include silicon-containing radical or a compound that forms a silicon-containing radical in the reaction system.

Specific examples of silicon-containing radical include, but are not limited to) the following radicals:

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The compound that can capture radicals, includes secondary amine.

Preferred can be called a secondary amine represented by the following General formula (IV):

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(where m represents an integer from 0 to 3, D and D' are each separately

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A, B, X1X2, R1, R2, R3, R4and W are each individually hydrogen or a replacement GRU is each carbon atom in the ring or the nitrogen atom in the ring may form a double bond between adjacent atoms).

Substituting group in the General formula (IV) may be the same as specified in example substitutional group X in the above General formula (II). Preferred examples of the hydrogen or replacement groups in the General formula (IV) are hydrogen, an alkyl group, aryl group, halogen, cyano, amino group, the group isothiocyanato acid, -COORa (where RA is hydrogen, alkyl group and aryl group), (di)acylaminoalkyl group, hydroxyl group, hydroxyalkyl group, alkoxygroup, arielalexisxrp, -CONRbRc (where Rband Rcare each separately a hydrogen, alkyl group and aryl group), exogroove (=O) group imide maleic acid group, phosphoric acid group = NH, or a divalent group.

Replacement group, which may be the same or different, may represent hydrogen atom, halogen atom, hydrocarbon group, a residue of heterocyclic compounds, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group or a silicon-containing group or a ring formed by at least two specified groups, connected to each other.

Preferred compounds of General formula (IV) are those in which all the characters R1, R2, R3and R4represent a group selected from alkyl groups. For example, they may include 2,2,6,6-tetraalkyllead, 2,2,6,6-tetraalkyl-4-piperidinol, bis-(2,2,6,6-tetraammineplatinum)sebacate or of 2.2.5.5-tetraalkylammonium or the specified connection, the above-mentioned substituted by the group.

Specific examples of the secondary amine include, but are not limited to) the following connections:

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As compounds that can capture radicals, can be called a complicated working fooly represented by the General formula (VIII):

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where p is an integer from 0 to 3, R12and R13are each separately substituting group, and Z represents hydrogen or another replacement group).

Is preferred when R12and R13represent an alkyl group having 1-30 carbon atoms, or aryl group having 1-30 carbon atoms, and Z represents hydrogen, halogen, the AK is specified as an example, substitutional group X in the above General formula (II).

Specific examples of the compounds of General formula (VIII) include (but are not limited to) the following connections:

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As compounds that can capture radicals include phosphine oxides. The phosphine oxides of the present invention include compounds of General formula (IX):

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(where R14, R15and R16are each separately hydrogen or other replacement group).

Preferably, R14, R15and R16represented alkyl or aryl group.

Substituting group in the General formula (IX) may be the same as specified in example substitutional group X in the above General formula (II).

Specific examples of the compounds of General formula (IX) include (but are not limited to) the following connections:

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In addition, in the method according to the present invention can use any phosphine oxide, stable at room temperature, or compound that is converted into phosphine oxide under the reaction conditions.

As a compound that is converted into phosphine oxide under the reaction conditions, can be called Soi individually hydrogen or other replacement group).

Substituting group in the General formula (X) may be the same as specified in example substitutional group X in the above General formula (II). It is desirable that these substituting groups represented alkyl or aryl group.

Specific examples of the compounds of General formula (X) include (but are not limited to, triphenylphosphine and tributylphosphine:

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As the compound that can capture radicals, can be used spinosaurus substance. Spinosaurus substance is a compound, which is used to identify the radical with a short life, which cannot be observed directly by EPR (electron paramagnetic (spin) resonance, ESR), and which forms together with the radical complex spinosaurus connection-radical, which allows to identify the initial radical with a short life time by analyzing the EPR study.

Specific examples of the compounds include (but are not limited to) Nitron and nitrosoguanidine below:

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In the present invention the hydrocarbon oxidation is carried out in the presence of at least one connection to dicale. Assuming that the connection is capable of capturing radicals seized the radical, we can determine the enthalpy (H) the relationship between the connection and the radical by the calculation method described below. Suitable range of H depends on the type of capture moiety, and its value can be used to select capable of capturing radicals of the compounds of the present invention.

Satisfactory results can be obtained when the compound that can capture radicals, such connection, the value of enthalpy (H) which is in the range from -30 to 50 kJ/mol in the calculation based on the assumption that captured the radical is the radical corresponding oxidizable hydrocarbon (formula 1-2). The value of enthalpy (H) is preferably from 25 to 50 kJ/mol and more preferably 20 to 50 kJ/mol. In accordance with the present invention the use of a compound that can capture those radicals, H which is specified a suitable interval, gives satisfactory results:

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Method of calculating H (enthalpy):

The calculation was carried out through structural optimization for the structure, showing Naeem (AM1 method: program MORAS) after conformational studies by molecular force field (force field method CHARMm: a program QUANTA).

The compound that can capture radicals, chosen in a suitable interval above (S), and in the present invention, the most preferred is the value of the enthalpy (H).

The following describes the reaction conditions of the present invention.

The amount used of the compound that can capture radicals, or compounds, which is transformed into a compound that can capture radicals in the reaction system in the present invention typically is in the range 0,00001-5.0 parts by weight, preferably in the range of 0.0001-0.1 parts by weight, per 100 parts (by weight) of raw hydrocarbons.

As the oxygen-containing gas as an oxidizing agent typically use air, but you can also use the oxygen, or any gaseous mixture of oxygen and nitrogen.

The reaction is usually carried out at atmospheric pressure, but can be done under reduced pressure. The reaction temperature is usually in the range of 40-120oWith, preferably in the range of 50-100oC.

Furthermore, the reaction can be carried out in the presence of a base in the form of solid or aqueous solution. Examples of bases include sodium carbonate, HYDR magnesium. The amount used in the reaction, the base is usually of 0.0001 to 10.0 parts by weight, preferably 0.001 to 5.0 parts by weight, per 100 parts by weight of raw hydrocarbons.

The reaction according to the present invention can be periodic or continuous manner. In the case of reaction of a periodic way, if the original hydrocarbon is a liquid at the reaction temperature, the above connection, capable of capturing radicals, or the above compound, which is transformed into a compound that can capture radicals in the reaction system, is introduced into the source material and carry out the oxidation reaction of the hydrocarbon by blowing air under heating and stirring. If necessary, the solvent in the reaction it is possible to use inert organic solvent. On the other hand, if the source arylalkyl hydrocarbons at the reaction temperature is a solid, it is dissolved in an inert organic solvent to form a solution and the above connection, capable of capturing radicals, or the above compound, which is transformed into a compound that can capture radicals in the Ki solution in the air while heating and stirring.

In addition, in accordance with the present invention in hydrocarbon optionally may contain a small amount of hydroperoxide corresponding to the hydrocarbon, as the initiator at the start of the reaction.

If necessary, you can also use a catalyst such as a complex of the transition metal.

Such a catalyst can be formed in the fixed layer can be omitted with formation of a mixture of raw hydrocarbon or its solution and air.

According to the method of the present invention formed hydroperoxide can be easily removed from the reaction mixture by distillation or any other traditional way by the end of the reaction and, if required, after filtering off the catalyst.

EXAMPLES

The following is a specific description of examples of preparation of organic hydroperoxides from arylalkyl hydrocarbon. However, the following examples by no means limit the present invention.

Example 1

To a mixture of 144 g cumene and 36 g of cumonherface was added 18 mg of 2,2,6,6-tetramethylpiperidine and it was all dissolved. To the resulting solution was added 90 g of 0.05% (by weight) CA is Ohm 400 ml/min with vigorous stirring for 3 hours to oxidize cumene.

Within 3 hours from the start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface, which amounted to 5.0 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which was 91 mol.%.

Was calculated and the enthalpy (H) used 2,2,6,6-tetramethylpiperidine and Khmilnyk radicals corresponding to Kumano, which were respectively 0.2 eV and sphere-6,4 kJ/mol.

Example 2

The reaction was carried out as in example 1, except that instead of 2,2,6,6-tetramethylpiperidine used di-tert-butylnitrone.

Within 3 hours from the start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface, which amounts to 5.2 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which was 90 mol.%.

Calculate the enthalpy (H) used di-tert-butylnitrone and Khmilnyk radicals corresponding to Kumano, which was -15,0 kJ/mol.

Within 3 hours from the start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of hydroperoxide, which amounted to 5.0 wt. % per hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which was 87 mol.%.

Example 4

The reaction was carried out as in example 1, except that instead of 2,2,6,6-tetramethylpiperidine used nitrosodimethyl potassium.

Within 3 hours from the start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface, which was 5.1 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which was 89 mol.%.

Example 5

To a mixture of 126 g cumene and 54 g of cumonherface was added 50 mg of 2,2,6,6-tetramethyl-4-piperidinol and it was all dissolved. To the resulting solution was added 5.6 g of distilled water and this mixture was heated at a pressure of 6 kg/m2) to 105oC. Oxidized of cumin by continuous reaction with a residence time of 1 hour between 5 and 6 hours after start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface and find its average value, which was 3.7 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction and find its average value, which was 92 mol.%.

Example 6

The reaction was carried out as in example 5, except that instead of 2,2,6,6-tetramethyl-4-piperidinol used 36 mg of bis-(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate.

4, 5 and 6 hours after start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface and find its average value, which was 3.8 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction and find its average value, which was 90 mol.%.

Example 7

To a mixture of 122 g cumene and 53 g of cumonherface was added 5 g of distilled water and 36 mg of 2,4,6-triphenylene and all this was dissolved to obtain an oil phase. The resulting mixture was heated at a pressure of 6 kg/m2) to 105oC. Komen oxidized, blowing air with a flow rate of 180 ml/min with vigorous stirring.

A solution of 36 mg of the flow respectively 175 g/h and 5 g/h, resulting in time during the continuous reaction was 1 hour. Later, 4 hours after start of the reaction every hour three times the reaction was poured the liquid into another vessel.

By iodometry and gas chromatography was determined by the rate of accumulation of cumonherface. The average value of three measurements was 3.8 wt. %/hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction. The average value of three measurements was 89 mol.%.

Calculated (SOMO) enthalpy (H) of 2,4,6-triphenylbenzene radical, presumably derived from 2,4,6-triphenylbenzene, and komileva radical corresponding to Kumano, which were respectively 0.4 eV and -16,5 kJ/mol.

Example 8

The reaction was carried out as in example 7, except that instead of 2,4,6-triphenylene used 2,6-di-tert-butyl-4-METHYLPHENOL.

By iodometry and gas chromatography was determined by the rate of accumulation of cumonherface. The average value of three measurements was 3.5 wt. %/hour. In addition, by high-performance liquid chromatography determined the selectivity obrazovaniya and 53 g of cumonherface was added 5 g of distilled water and 36 mg of triphenylphosphine and all this was dissolved to obtain an oil phase. The resulting mixture was heated at a pressure of 6 kg/m2) to 105oC. To oxidize cumene was piercing the air with a flow rate of 180 ml/min with vigorous stirring.

A solution of 36 mg of triphenylphosphine in a mixture of 122 g cumene and 53 g of cumonherface and distilled water was introduced into the reactor at a flow rate respectively 175 g/h and 5 g/hour, resulting in time during the continuous reaction was 1 hour. Later, 4 hours after start of the reaction every hour three times the reaction was poured the liquid into another vessel.

By iodometry and gas chromatography was determined by the rate of accumulation of cumonherface. The average value of three measurements was 4.5 wt. %/hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction. The average value of three measurements was 90 mol.%.

Example 10

The reaction was carried out as in example 9, except that instead of triphenylphosphine used three-tert-butylphosphine.

By iodometry and gas chromatography was determined by the rate of accumulation of cumonherface. The average value of three measurements was 3.5 wt. wounded in the course of the reaction codingerroraction, which was 90 mol.%.

Comparative example 1

The reaction was carried out as in example 1, except that 2,2,6,6-tetramethylpiperidinyloxy not used.

Within 3 hours from the start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface, which was 5.5 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which amounted to 84 mol.%.

Comparative example 2

The reaction was conducted as in comparative example 1, except that the reaction temperature was set at 100oC.

Within 3 hours from the start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface, which was 4.1 wt. % per hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which was 88 mol.%.

Comparative example 3

The reaction was carried out as in example 5, except that 2,2,6,6-tetramethyl-4-piperidinol not ispolzovat accumulation cumonherface, which was 5.5 wt. % per hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which amounted to 86 mol.%.

Comparative example 4

The reaction was conducted as in comparative example 3, except that the reaction temperature was set at 100oC.

4, 5 and 6 hours after start of the reaction was determined by means of iodometry and gas chromatography the rate of accumulation of cumonherface and find its average value, which was 3.9 wt.% in the hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction and find its average value, which was 89 mol.%.

Comparative example 5

The reaction was carried out as in example 7, except that 2,4,6-triphenylene not used.

By iodometry and gas chromatography was determined by the rate of accumulation of cumonherface. The average value of three measurements was 5.5 wt. %/hour. In addition, by high-performance liquid chromatography determined the selectivity R>
The reaction was conducted as in comparative example 5, except that the reaction temperature was set at 100oC.

By iodometry and gas chromatography was determined by the rate of accumulation of cumonherface. The average value of three measurements was 3.9 wt. %/hour. In addition, by high-performance liquid chromatography determined the selectivity formed during the reaction codingerroraction, which was 88 mol.%.

1. The method of producing hydroperoxides, comprising the oxidation of a hydrocarbon of the following formula (I)

< / BR>
where P and Q which can be the same or different from each other, represent hydrogen or alkyl group;

x is an integer of 1-3;

AG - aromatic hydrocarbon group,

oxygen-containing gas in the presence of at least one compound that can capture radicals selected from

a) the compounds of formula (II) or a compound that forms a compound of formula (II) in the reaction system

< / BR>
where Z is sulfur or phosphorus;

X - proxy group;

n is an integer of 1-4,

b) compounds of the formula (III) or (IV), or a compound that forms a compound of formula (III who con

< / BR>
A, B, X1X2, R1, R2, R3, R4and W are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen, and each carbon atom in the ring or the nitrogen atom in the ring may form a double bond between adjacent atoms,

c) radical phosphorus, or a compound that forms a radical of phosphorus in the reaction system;

d) phosphine oxide, or a compound which forms an oxide phosphine in the reaction system;

e) a sulfur radical, or a compound that forms a radical of sulfur in the reaction system;

(f) radical carbon, or a compound that forms a radical of carbon in the reaction system;

(g) radical silicon, or a compound that forms a radical of silicon in the reaction system,

(h) compounds, which forms nitroxide radical, in a reaction system, which is selected from compounds represented by formulas (V), (VI) and (VII)

< / BR>
where n is an integer 0-4;

R5and R6are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, and substituting group, containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen,

< / BR>
where l is an integer of 0-3;

Y, R10and R11are each individually hydrogen or a replacement a group containing an element selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, silicon and halogen,

(i) nitroxide radical of any of the following formulas (1) to(8)

< / BR>
< / BR>
< / BR>
< / BR>
2. The method according to p. 1, in which arylalkyl hydrocarbons of the General formula (I) represents cumin, cimen, m-diisopropylbenzene, p-diisopropylbenzene, 1,3,5-triisopropylbenzene, isopropylnaphthalene, diisopropylnaphthalene, isopropylphenyl, diisopropylphenyl or a mixture of two or more of these compounds.

3. The method according to p. 2, in which arylalkyl hydrocarbon is cumin.

4. The method according to p. 1, in which the compound that can capture radicals is a compound represented by the formula (III) or (IV), in which two or more structures of the formula (III) or (IV), respectively transversely sewn by any group selected from the X1X2, A and B.

5. The method according to p. 1, in which the compound that can capture radicals, predy separately represent hydrogen, alkyl group, aryl group, halogen, a cyano, an amino group, a group isothiocyanato acid, -COORa, where Ra is hydrogen, alkyl group or aryl group, (di)acylaminoalkyl group, hydroxyl group, hydroxyalkyl group, alkoxygroup, arielalexisxrp, -CONRbRc, where Rb and Rc are each separately a hydrogen, alkyl group and aryl group, oxoprop (=O) group imide maleic acid group, phosphoric acid or the group =NH.

6. The method according to p. 1, in which the compound that can capture radicals is a compound of formula (III) or (IV) in which R1, R2, R3and R4represent an alkyl group.

7. The method according to p. 6, in which the compound represented by the General formula (III) is 2,2,6,6-tetraammineplatinum-oxely radical, 4-hydroxy-2,2,6,6-tetraammineplatinum-oxely radical, bis-(2,2,6,6-tetraammineplatinum)sebacate or of 2.2.5.5-tetraalkylfuranidones radical.

8. The method according to p. 6, in which the compound represented by the General formula (IV) is 2,2,6,6-tetraalkyllead, 2,2,6,6-tetraalkyl-4-piperidinol, bis-(2,2,6,6-tetraammineplatinum)sebacate or of 2.2.5.5-tetraalkylammonium.

10. The method according to p. 9, in which the difference in energy levels SOMO ((SOMO)) between the compound that can capture radicals, and captured by radicals is not more than 10 eV in the calculation method MNDO-PM3.

11. The method according to p. 1, in which the difference between the energy level of the SOMO ((SOMO) of the compound that can capture radicals, and the energy level of the SOMO of the radical calculated using the MNDO-PM3 is 0-10 eV and the radical corresponds to oxidize the hydrocarbon and is represented by the formula (1-2)

< / BR>
where P and Q represents hydrogen or alkyl group may be the same or different;

x is an integer 1-3 and ar represents an aromatic hydrocarbon group.

12. The method according to any of paragraphs.1 and 9-11, in which the compound that can capture radicals, is the magnitude of the calculated enthalpy (H) 30-50 kJ/mol and this is enough to break the connection between the specified compound that can capture radicals, and the radical of the formula (1-2) p. 11, which corresponds to oxidize the hydrocarbons.

 

Same patents:

The invention relates to a method of cumene oxidation in aqueous-alkaline emulsion in which is used a cascade of reactors, is obtained by dividing the reactor of the cascade of two stages, the first stage, containing less than 18% by weight of cumene hydroperoxide, as an active carbonate is used NH4NaCO3and in the second stage, containing more than 18% by weight of cumene hydroperoxide, as an active carbonate use Na2CO3

The invention relates to the field of industrial manufacture of products of petrochemical synthesis, in particular to a process for the production of cumene hydroperoxide for its subsequent decomposition to phenol and acetate

The invention relates to a method for producing aliphatic and alkylaromatic hydroperoxides, which are widely used, for example, epoxidation of olefins, upon receipt of phenol and carbonyl compounds (acetone, acetaldehyde, etc.)
The invention relates to the petrochemical industry and can be used in the process of joint production of propylene oxide and styrene
The invention relates to the petrochemical industry and can be used in the process of joint production of propylene oxide and styrene

The invention relates to a reactor unit to obtain gidroperekisi ethylbenzene oxidation of ethylbenzene oxygen-containing gas (oxygen) and can be used to obtain, respectively, of hydroperoxides of isobutane and isopentane

The invention relates to the petrochemical industry and can be used in the process for the joint production of propylene oxide and styrene

The invention relates to a method for producing aliphatic and alkylaromatic hydroperoxides, which are widely used, for example, epoxidation of olefins, upon receipt of phenol and carbonyl compounds (acetone, acetaldehyde, etc.)

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of alkylaryl hydroperoxides useful as starting material in production of propylene oxide and alkenylaryl. Process of invention comprises following stages: oxidation of alkylaryl compound to form reaction product containing alkylaryl hydroperoxide; contacting at least part of reaction product with basic aqueous solution; separation of hydrocarbon phase containing alkylaryl hydroperoxide from aqueous phase; containing at least part of above hydrocarbon phase with aqueous solution containing waste water, said aqueous solution containing less than 0.2% alkali metal and/or salt (determined as ratio of metal component to total amount of solution); and separation of hydrocarbon phase from aqueous phase. By bringing at least part of above hydrocarbon phase containing alkylaryl hydroperoxide into interaction with propylene and catalyst, alkylaryl hydroxide and propylene oxide are obtained. At least part of propylene oxide is then separated from alkylaryl hydroxide. Dehydration of at least part of alkylaryl hydroxide results in formation of alkenylaryl.

EFFECT: reduced amount of contaminating by-products in alkylaryl hydroperoxide preparation stage.

8 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining cyclohexyltoluene hydroperoxide, which can serve as source of joint obtaining of cresols and cyclohexanon and as initiator of emulsion polymerisation of unsaturated hydrocarbons. According to claimed method obtaining of cyclohexyltoluene hydroperoxide is carried out by oxidation of cyclohexyltoluene with air oxygen at atmospheric pressure in presence of catalyst N-hydroxyphtalimide at temperature of process 110-140°C, during 2-3 hours until content of cyclohexyltoluene hydroperoxide is 22.2%.

EFFECT: increase of target product formation rate, reduction of process duration and reduction of power consumption for its carrying out.

1 cl, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to the method for preparation of cyclohexylisopropylbenzene hydroperoxide which can be used as initiator of unsaturated hydrocarbons emulsion polymerisation. According to the invention cyclohexylisopropylbenzene hydroperoxide is prepared by oxidation of cyclohexylisopropylbenzene with air oxygen at temperature 100-120°C and atmospheric pressure during 1-3 hrs in the presence of catalyst N-hydroxyphthalimide up to cyclohexylisopropylbenzene hydroperoxide concentration 64%.

EFFECT: enhancing of the cyclohexylisopropylbenzene hydroperoxide formation rate; decrease of the process time and energy consumption.

1 cl, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to the method for preparation of cyclohexyl-o-xylol hydroperoxide which can be used as the source of combined obtaining of xylenols and cyclohexanone and as the initiator of emulsion polymerisation of unsaturated hydrocarbons. According to the invention cyclohexyl-o-xylol hydroperoxide is prepared by oxidation of cyclohexyl-o-xylol with air oxygen at temperature 100-150°C and atmospheric pressure in the presence of catalyst N-hydroxyphthalimide during 1-3 hrs. up to cyclohexyl-o-xylol hydroperoxide concentration 34%.

EFFECT: enhancing of the cyclohexyl-o-xylol hydroperoxide formation rate; decrease of the process time and energy consumption during oxidation process.

1 cl, 2 tbl, 2 ex

FIELD: pharmacology.

SUBSTANCE: invention concerns cyclic hydrocarbons, particularly obtainment of cyclohexyl-p-xylol hydroperoxide, which can serve as source for simultaneous xylenol and cyclohexanol obtainment and as emulsion polymerisation initiator for unsaturated hydrocarbons. Cyclohexyl-p-xylol hydroperoxide is obtained by cyclohexyl-p-xylol oxidation by air oxygen at atmospheric pressure in the presence of N-hydroxyphthalamide catalyst in amount of 0.5-2.5 wt % and process temperature of 110-150°C for 1-3 hours till cyclohexyl-p-xylol hydroperoxide content reaches 9.8%.

EFFECT: reduced duration of oxidation process, reduced power cost.

1 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical industry and can be used in combined production of styrene and propylene oxide. Ethylbenzene hydroperoxide is obtained in accordance with the invention by oxidising ethylbenzene with atmospheric oxygen in a continuous reactor at atmospheric pressure in the presence of N-hydroxyphthalimide as a catalyst in amount of 0.5-3 wt % and temperature of the process of 125-130°C until achieving content of ethylbenzene hydroperoxide of 19.2%.

EFFECT: increased conversion of ethylbenzene and selectivity of the process.

1 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of hydroperoxides of alkylaromatic hydrocarbons which can serve as a source of oxygen-containing organic compounds (phenol, methylphenols, acetone, cyclohexanone etc) and as an initiator of emulsion polymerisation of unsaturated hydrocarbons. The invention discloses a method for synthesis of hydroperoxides of alkylaromatic hydrocarbons through liquid-phase oxidation of these hydrocarbons with atmospheric oxygen at atmospheric pressure, process temperature of 110-130°C, for 1-3 hours in the presence of a 4-methyl-N-hydroxyphthalimide catalyst in amount of 1.0-2.0 wt %.

EFFECT: catalyst prevents use of an initiator and alkaline additives, which considerably simplifies the process, higher conversion of initial alkylaromatic hydrocarbons while preserving high selectivity of the process.

2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for liquid-phase oxidation of ethylbenzene to ethylbenzene hydroperoxide, where concentration of ethylbenzene hydroperoxide is kept below 20 wt % with respect to total weight of the reaction mixture and where styrene and/or a styrene derivative is added to ethylbenzene. Concentration of said styrene and/or styrene derivative can range from 0.01 to 5.0 wt %. The styrene derivative is a styrene derivative in which one or more unsubstituted carbon atoms of the styrene have an alkyl group and/or a halogen atom as a substitute. The invention also relates to a method of producing an alkylene oxide, preferably styrene and propyelene oxide.

EFFECT: improved method.

10 cl, 3 dwg, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining n-cemene hydroperoxide, which can be used for combined production of cresol and acetone. In accordance with invention claimed is method of obtaining n-cymene hydroperoxide by liquid-phase oxidation of n-cymene with air oxygen at atmospheric pressure, temperature of the process 80-110°C, for 1-3 hours, in presence of N-hydroxyphthalimide as catalyst in amount 1-5 wt %, until content of n-cymene hydroperoxyde is 25-28%.

EFFECT: catalyst excludes application of initiator and alkaline additives, which simplifies the process considerably; high rate of n-cymene oxidation is achieved.

1 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of separating monoalkylbenzene from gas flow, including oxygen and monoalkylbenzene, in which gas flow, including oxygen and monoalkylbenzene, contacts with liquid flow, including naphthalene compound. In addition, claimed invention relates to method of obtaining alkylphenylhydroperoxide, including said monoalkylbenzene separation.

EFFECT: method makes it possible to separate monoalkylbenzene in effective and selective way.

12 cl, 1 ex, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns method of isopropylbenzene hydroperoxide (IPBHP) concentration, applied in phenol and acetone production by isopropylbenzene method. The claimed method involves feed of oxidate for rectification into a vessel with gas phase separation in top part or into condensers of rectification columns.

EFFECT: reduced load on columns, enhanced column efficiency, reduced loss of IPBHP with distillate, power saving.

3 cl, 2 dwg, 3 tbl, 3 ex

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