The method of obtaining aliphatic or alkylaromatic hydroperoxides

 

(57) Abstract:

Usage: in the process of epoxidation of olefins upon receipt of phenol and carbonyl compounds. The inventive receiving aliphatic or alkylaromatic hydroperoxides. Reagent 1: the corresponding hydrocarbon. Reagent 2: oxygen-containing catalyst. Reaction conditions: reagent 1 is treated with the reagent 2 in the presence of a cobalt containing catalyst is a fluoride-containing organic salt of cobalt, selected from a particular group. The process is conducted in the presence of alcohol, the corresponding oxidizable hydrocarbon. Before oxidation, the reaction mass is maintained at the reaction temperature for 5 to 15 minutes table 2.

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.).

A method of obtaining cumene cumene oxidation of cumene with oxygen or oxygen-containing gases in the presence of a catalyst complex of cobalt and-naphtylamine.

The disadvantage of this method SOS is Yunosti process on the target product.

There is also known a method of producing hydroperoxides aliphatic hydrocarbons by oxidation of aliphatic hydrocarbons in liquid or gas phase with oxygen or kislorodsodyerzhascimi gas in the reactor, the surface of which is coated with titanium or its alloys, playing the role of a catalyst at a temperature of 120-150aboutC and a pressure of 30-50 bar.

The disadvantage of this method is the low value of the conversion of aliphatic hydrocarbons and selectivity of the formation of the corresponding hydroperoxide.

The closest in technical essence and the achieved result is a method of producing ethylbenzene hydroperoxide by oxidation of ethylbenzene oxygen-containing gas at a temperature of 120aboutC for 3-4 h in the presence of a catalyst of cobalt stearate, manganese, chromium, copper or Nickel, or acetylacetonates or dimethylbenzoic cobalt, taken at a concentration of 1 to 10-31 10-2mol/H. Best results are 18-20 mol. selectivity to hydroperoxide with the degree of conversion of the hydrocarbon to 35% [1]

The disadvantage of this method is the low selectivity to ethylbenzene hydroperoxide.

The objective of the invention is to provide a process which agrees method of obtaining organic hydroperoxides by the oxidation of aliphatic or alkylaromatic hydrocarbon with oxygen or oxygen-containing gas at an appropriate elevated temperature in the presence of a cobalt containing catalyst, where as cobalt containing catalyst is used organofluorine salt of cobalt selected from the group: (CF3(CH2)nCOO)3, Co(CF3(CH2)nCOO)2, CO(CF3(CF2)nCOO)3, CO(CF3(CF2)nCOO)2, Co F(CH3(CH2)nCOO)2, CO F(CH3(CH2)nCOO), Co F(CF3(CH2)nCOO)2, Co F(CF3(CH2)nCOO), Co F2(CH3(CH2)nCOO), Co F2(CF3(CH2)nCOO), where n is 0-11, or a mixture of salts of this group, the oxidation is carried out in the presence of alcohol, the corresponding oxidized hydrocarbon, at a concentration of 5 10-45 10-3mol/l and cobalt salts at a concentration of 1 to 10-51 10-4mol/l, and before the oxidation reaction mass is maintained at the reaction temperature for 5-15 minutes

Adherence to the stated conditions can improve the selectivity of the conversion of hydrocarbons to the corresponding hydroperoxide to 74-91 mol. when the degree of conversion of the hydrocarbon from 14,3 to 27.1% in this second commercial product is the corresponding alcohol, the selectivity by which depending on the selected conditions is from 6 to 17 mol.

Compounds of General is of cobalt carbonyl with the respective perforated acids [2] Co(CF3(CF2)nCOO)3, Co(CF3(CH2)nCOO)3synthesized from water-soluble salts With3+and sodium (potassium) salts of the respective perforated acids [3] Compounds of this type may be used as catalysts for the oxidation of unsaturated hydrocarbons [3]

Compounds of General formula CoF(CH3(CH2)nCOO)2, CoF(CH3(CH2)nCOO), CoF(CF3(CF2)nCOO)2, Co F(CF3(CF2)nCOO), Co F2(CH3(CH2)nCOO), Co

F2(CF3(CF2)nCOO) receive the action of hydrogen fluoride on the combination of the first two types. Their characteristic feature is the presence of communication Co-F, giving in IR-spectra characteristic band of stretching vibrations at 725 cm-1[4]

P R I m e R 1. The oxidation is carried out in a glass reactor bubbling type, equipped with electric shell, reflux condenser, flagmaterial and sampler. The temperature oxidation constant support. Stirring is carried out using air or oxygen, the flow rate adjust the rotameter.

The reaction is carried out as follows: the reactor is placed 0,021 g trifenatate Kobalt>aboutC and maintained for 7 min at a flow of nitrogen. Then the reactor start feeding the air with a flow rate of 0.6 l/min, the Concentration of cobalt salts is 5 10-5mol/l, the concentration of alcohol 5 10-3mol/L. oxidation of the lead 3 h at 120aboutC. Then the reaction mass is then cooled and analyzed by GLC and iodometrically on the content of hydroperoxide. The conversion of ethylbenzene to 17.5% was formed 24,38 g of ethylbenzene hydroperoxide. Selectivity to hydroperoxide 82% also received a 2.36 g methylphenylcarbinol, the selectivity for the resulting alcohol 9%

The resulting oxidate is a commodity product. If desired, the ethylbenzene hydroperoxide can be distinguished from oxidate in the form of sodium salt, with subsequent decomposition of HCl to pH 5-6, the ethyl ether extraction, distillation of the ether and distillation in vacuum at a residual pressure of 0.15 mm RT.article Allocated thus the product has a purity of 98.9 per cent of its number 23,06,

P R I m m e R 2. The oxidation of lead in example 1, but as oxidant use oxygen, duration of experience is 1.5 hours-Degree of conversion of ethylbenzene to 19.3% selectivity to hydroperoxide 81 mol.

The results of examples 3-31 summarized in table. 1 and 2.

the hydrogen in the hydroperoxide to the values 90-91 mol. in optimal conditions, when the degree of conversion of up to 25% Reduction or absence of alcohol in the reaction mass (examples 33** 35**), the excess or decrease in the concentration of cobalt catalyst (examples 33* and 34**) leads to lower selectivity. Reducing the exposure time reduces the degree of conversion of the hydrocarbon (example 29**), the increase in economic is not justified (example 30**).

Thus, the claimed method allows to achieve high values of selectivity to hydroperoxide, this significantly increases the speed of the process, which allows in aggregate industrial to carry out this method.

The METHOD of OBTAINING ALIPHATIC OR ALKYLAROMATIC HYDROPEROXIDES by the oxidation of hydrocarbons oxygen-containing gas at elevated temperature in the presence of a cobalt containing catalyst, characterized in that as a cobalt containing catalyst is used organofluorine salt of cobalt selected from the group: Co[(CF3(CH2)nCOO]3, Co[CF3(CH2)nCOO]2, Co[CF3(CF2)nCOO]3, Co[CF3(CF2)nCOO]2, CoF[CH3(CH2)nCOO]2, CoF[CH3(CH2)nCOO,

CoF[CF33(CH2)nCOO]

CoF2[CF3(CF2)nCOO] where n 0 11 at a concentration of 1 to 10-51 10-4mol/l, and the process is conducted in the presence of alcohol, the corresponding oxidizable hydrocarbon at a concentration of 5 10-45 10-3mol/l, and before the oxidation reaction mass is maintained at the reaction temperature for 5 to 15 minutes

 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for synthesis of organic hydroperoxide comprising the reduced amount of impurities. Method involves the following steps: (a) oxidation of organic compound to yield the reaction product comprising organic hydroperoxide; (b) contacting at least part of the reaction product comprising organic hydroperoxide with the basic aqueous solution; (c) separation of hydrocarbon phase containing organic hydroperoxide from an aqueous phase; (d) washing out at least part of the separated hydrocarbon phase containing organic hydroperoxide, and (e) contacting at least part of hydrocarbon phase containing organic hydroperoxide with a protective layer comprising a solid adsorbent wherein a solid adsorbent shows porosity 50-98% by volume. Except for, invention proposes a method for preparing oxirane compound from hydrocarbon phase obtained at the step (e) by the method described above and containing alkylaryl hydroperoxide. The presence of the protective layer reduces the pressure increment in the catalyst layer that is caused by the declined content of impurities in the raw comprising alkylaryl hydroperoxide.

EFFECT: improved preparing method.

7 cl, 2 ex

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: organic chemistry, chemical technology.

SUBSTANCE: invention relates to method for synthesis of alkylaryl peroxide-containing compound. Method involves the following steps: (a) oxidation of alkylaryl compound to yield the alkylaryl hydroperoxide-containing reaction substance; (b) treatment of at least part of the reaction substance containing alkylaryl hydroperoxide synthesized at the step (a) wherein this the reaction product comprises less 0.05% of sodium (by mass); (c) separation of product synthesized at the step (b) for hydrocarbon phase containing alkylaryl hydroperoxide and an aqueous phase; (d) repeating steps (b) and (c) by one or some time being optionally. Also, synthesis of alkylaryl hydroxide involves the additional treatment step (e) of at least part of hydrocarbon phase containing alkylaryl hydroperoxide synthesized at steps (c) or (d), olefin and a catalyst to yield alkylaryl hydroxide and oxirane compounds, and (f) separation of at least part of oxirane compound from alkylaryl hydroxide. Synthesis of alkenylaryl involves the additional step (g) of dehydration of at least part of alkylaryl hydroxide synthesized at step (f). Invention provides simplifying the technological process resulting to synthesis of improved substance containing alkylaryl hydroperoxide from which alkylaryl hydroxide is prepared followed by preparing alkenylaryl.

EFFECT: improved method of synthesis.

11 cl, 1 tbl, 6 ex

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

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 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 a method of producing isopropyl benzene hydroperoxide (IPB HP) which is then used to produce phenol and acetone using what is known as industrial cumol method. According to the invention, isopropyl benzene hydroperoxide is obtained by oxidising isopropyl benzene with molecular oxygen. The catalyst used is iron nanopowder with specific surface area of 6.9 m2/g, obtained through electrical explosion of a conductor in a nitrogen atomsphere. The process is carried out at 50-60°C.

EFFECT: increased output of isopropyl benzene hydroperoxide.

1 cl, 3 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 the technology of producing peroxyacids which can be used in delignification and bleaching cellulose materials in the textile industry. The method of preparing a peroxyacid solution for delignification and bleaching involves reaction of acetic acid and hydrogen peroxide in equimolar amounts in the presence of an acid catalyst - sulphuric acid and organophosphonate-nitriletrimethylene phosphonic acid with ozonation, with ozone consumption of 1-4 g/h.

EFFECT: high output of peroxyacid and high efficiency during delignification and bleaching.

1 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing cyclic geminal bis-hydroperoxides from ketones with ring size C12-C15 used to produce 1,2,4,5-tetraoxanes having high anti-parasitic activity. Cyclic geminal bis-hydroperoxides can also be used as radical polymerisation initiators. The disclosed method of producing C12-C15 cyclic geminal bis-hydroperoxides involves reaction of corresponding C12-C15 cycloalkanones with hydrogen peroxide in the presence of boron trifluoride in an ether medium in molar ratio C12-C15 cycloalkanone:boron trifluoride:hydrogen peroxide equal to 1:0.8-1.2:7-12.

EFFECT: method enables to obtain C12-C15 cyclic geminal bis-hydroperoxides in a single step and simplifies and lowers the cost of the process, cuts reaction time, as well as labour, material- and power consumption when producing bis-hydroperoxides; method enables to obtain desired products with high output and high selectivity.

1 cl, 1 tbl, 8 ex

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

Up!