Propylene epoxidation process

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to technology of epoxidation of unsaturated compounds with hydrogen peroxide, in particular to production of propylene oxide and propylene glycol. Epoxidation is conducted in presence of organic solvent and catalytically active compound including zeolite catalyst. Product mixture contains propylene oxide, unreacted propylene, and α-hydroperoxypropanols, which are reduced with hydrogen into corresponding propylene glycols. As organic solvent, alcohols, preferably methanol, or their mixtures with water are used. Propylene oxide as well as unreacted propylene and solvent are separated by distillation at column vat temperature below 80°C and residence time less than 4 h. Hydrogenation catalyst is selected from group comprising heterogeneous catalysts containing as active metal Ru, Ni, Co, Pd, and Pt, individually or as two- or more-component mixture on suitable carrier.

EFFECT: enabled processing of hydroxyperoxyalcohol, epoxidation reaction by-product, into glycols so improving economical characteristics of the process.

15 cl, 3 ex

 

The present invention relates to a method for producing epoxide (epoxydecane). In the framework of the method according to the invention carry out the processing of the reaction mixture formed by the interaction of organic compounds having at least one double carbon-carbon bond with hydrogen peroxide in the presence of at least one catalytically active compound and one solvent in such a way that formed as a by-product of the epoxidation α-hydroperoxidase remain largely undecomposed, respectively, are converted to corresponding glycols.

The epoxides are called connection, which is produced by reaction of the joining of oxygen to both carbon atoms of the double bond.

When known from the prior art how to be epoxydecane connection, typically with at least one carbon-carbon double bond is subjected to interaction with hydrogen peroxide in a solvent, for example methanol, in the presence of a catalyst in an appropriate reactor. General principles the reaction of interaction described in the application DE 19835907.1, 10032885.7 and 10015246.5.

The resulting epoxide with subject epoxydecane unreacted compound, oxygen and other low-boiling by-products, and also with a small amount of process is Italia separated during distillation processing at the head of the column. In the lower part of the column distillation remains a mixture that consists mainly of solvent, water, unreacted hydrogen peroxide, and high-boiling by-products. This mixture can again be subjected to interaction with the subject epoxydecane connection. The flow of product is obtained with a mixture that consists mainly of a solvent, water, epoxide and by-products.

To get the target epoxide in its pure form, the head stream of the distillation columns, and paged the product additional reactor is subjected to further processing.

The most important by-products that are formed when epoxydecane represent, along with oxygen, the products, which may be formed in the reactions of addition of the solvent, water or hydrogen peroxide to obtain the epoxide. As an example, should be alkoxysilyl, glycols, as well as α-hydroperoxidase.

If the solvent used methanol and subject to epoxydecane compound is propene, as an important by-product of the above type are formed 2-methoxypropanol-1 and 1-methoxypropanol-2, propylene glycol, 2-hydroperoxidation-1 and 1-hydroperoxidation-2.

While methoxypropanol and propylene glycol are the Xia very stable molecules, hydroperoxidation as thermally unstable molecules are prone to decomposition with the formation of other by-products, among others, formaldehyde, acetaldehyde, propylene glycol, as well as hydroxyacetone. Some of these side products in addition prone to decomposition in the secondary by-products. For example, formaldehydefree, formic acid and methylformate formed from formaldehyde and acetylcholineesterase, acetic acid and methyl acetate from acetaldehyde.

Some of these secondary products cause the further processing of the mixture is particularly large problem. So, for example, substances such as acetaldehyde and methylformate can zatrudnienia be separated from the containing epoxide mixture.

In the patent US 6024840 describes associated with the high costs of equipment allocation method of acetaldehyde from propylene oxide by using a number of series-connected columns extractive, respectively, fractionated distillation.

Because lying close to each other boiling points of methylformate and propylene oxide in their separation requires a large amount of equipment. For example, in patent US 5170002 describes the Department of methylformate using a basic ion exchange resin, and only the formate reacts with the ion exchange smaoui it is removed.

Also the regeneration and recycling of valuable substances from the reaction mixture and their use for epoxidation still were associated with a high expenditure of funds on equipment due to the presence of by-products.

For example, when the epoxidation reaction the solvent used is preferably methanol. From economic considerations tend to regenerate from the system paged product, clear, and again to return to the process. Especially the presence often present in the reaction mixture of by-products such as acetaldehyde, acetylcholineesterase and methylformate, lead to technical problems. Almost complete separation of these interfering substances is still achieved only with high equipment costs.

For example, in patent US 5863391 describes such a method in which the separating acetaldehyde from methanol with satisfactory results can only be achieved by extractive distillation in several series of distillation columns. Also in the application DE 10032885.7 describes a very complex way to separate methylformate from methanol.

In accordance with the present invention is to develop a method, which completely prevents the formation of such difficult recyclable poboon the x products when epoxydecane, accordingly, reduces it to a minimum and thus eliminates existing in the known solutions to the problem.

Thus the invention relates to a method for the epoxidation of organic compounds having at least one double carbon-carbon bond with hydrogen peroxide in the presence of at least one catalytically active compound and at least one solvent, which is that the reaction mixture containing the α-hydroperoxidase, restore using at least one reductant.

Under organic compounds with at least one double carbon-carbon bond in the framework of the invention refers to all organic compounds that have at least one double carbon-carbon group.

In the framework of the invention preferably use organic compounds of the class of alkenes, which have at least one such group.

In the framework of the invention as alkenes are preferably used propene.

As an example, you can include the following alkenes:

Aten, propene, 1-butene, 2-butene, isobutene, butadiene, Panten, piperylene, hexene, hexadiene, hapten, octene, Diisobutyl, trimethylpentane, none, dodecan, tridecen, Tetra - to achozen, three - and tetrapropyl, polybutadiene, polyisobutene, and open, terpenes, geraniol, linalool, minalrestat, methylenecyclopropane, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxy, vinylcyclohexane, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, inden, tetrahydroindene, methylsterol, Dicyclopentadiene, divinylbenzene, cyclododecene, cyclododecatriene, Steven, diphenylbutadiyne, vitamin a, betacarotene, vinylidenefluoride, arilgalogenide, Cotillard, metallicgold, dichlorobutene, allyl alcohol, metalloy alcohol, butanol, butanediol, cyclopentanediol, pentanol, octadienal, tridecanol, unsaturated steroids, ataxite, isoeugenol, anethole, unsaturated carboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, feniluksousna acid, unsaturated fatty acid series, such as, for example, butyric acid, linoleic acid, palmitic acid, natural fats and oils.

Preferably in the method according to the invention are applied alkenes, which contain from 2 to 18 carbon atoms.

For the above epoxidation of organic compounds with at least one double carbon-carbon bond in the framework of the present invention is applied hydrogen peroxide.

Apply the hydrogen peroxide can be obtained using antrahinonovye way is by which you will get almost all the quantity produced in the world of hydrogen peroxide. This method is based on the catalytic hydrogenation of antrahinonovye connection with obtaining anthrahydroquinone connection, the subsequent interaction of the latter with oxygen to produce hydrogen peroxide and the final separation of the formed hydrogen peroxide via extraction. Catalyst closed loop re-hydrogenation of the remaining antrahinonovye connection.

Review antrahinonovye methods available in the publication "Ullmanns Encyclopedia of Industrial Chemistry", 5th edition, volume 13, str to 456.

It is also possible to obtain hydrogen peroxide to translate sulfuric acid anodic oxidation with simultaneous cathodic hydrogen evolution in peroxidizing acid. Hydrolysis peroxidizing acid then leads through peroxisomal acid to hydrogen peroxide and sulfuric acid, which it is regenerated.

Needless to say it is possible for the hydrogen peroxide from the elements.

Before applying hydrogen peroxide in the method according to the invention to be purchased, for example, by commercial solution of hydrogen peroxide can be free from unwanted ions. This can be used, among other things, the methods described, for example, in the application WO 98/54086, DE-A 4222109 or WO 92/06918. Also, at least salt, which is contained in the hydrogen peroxide solution may be removed from the ion solution is the exchange using the device, which differs in that it has at least one sour ion exchange layer with the cross-sectional area of flow F and height H, the height H of the ion exchange layer is less than or equal to 2.5·F1/2and, in particular, less than or equal to 1.5·F1/2. In the framework of the present invention can be applied to all sour ion-exchange layers with the cation and/or anion-exchange material. Also within one ion exchange layer cation-exchange and anion-exchange substances can be used as a so-called mixed layer. In one preferred form of the invention uses only one type of sour ion-exchange substances. Further preferably, applying basic ion exchangers, in particular basic anion-exchange substances and particularly preferably a weakly basic anion exchange substance.

The interaction of organic compounds having at least one double-bond, with hydrogen peroxide is carried out in the presence of at least one catalytically active compounds.

In General, in the framework of the present invention is suitable all well-known specialist in this area of the catalysts. Preferably used zeolite catalysts.

Thus the invention relates to a method of the above type, characterized in that m is Nisha least one catalytically active connection comprises a zeolite catalyst.

Zeolites are known crystalline aluminosilicates with uporyadochennoi channel and cell (prismatic) structure, which has micropores, which preferably less than ~ 0.9 nm. The mesh structure of zeolites is built on the tetrahedra of SiO4and AlO4that are linked by oxygen bridges. An overview of known structures can be found in the publication W.M.Meier, D.H.Olson und Ch.Baerlocher, "Atlas of Zeolithe Structure Types", ed. Elsevier, 4th edition, London. 1996.

Also known zeolites which contain no aluminum and which silikatnoi lattice instead of Si(IV) partially have titanium as Ti(IV). Titanium zeolites, in particular zeolites with crystal structure type MFI, as well as the possibility of obtaining them are described, for example, in application EP-A 0311983 or EP-A 405978. In addition to silicon and titanium, such materials can also contain additional elements, such as aluminum, zirconium, tin, iron, cobalt, Nickel, gallium, boron or small amounts of fluorine. In regenerated by the method according to the invention zeolite catalysts titanium may be partially or completely replaced by vanadium, zirconium, chromium or niobium or a mixture of two or more of the above elements. The molar ratio of titanium and/or vanadium, zirconium, chromium or niobium to summes silicon and titanium, and/or vanadium and/or zirconium and/or chromium and/or niobium, as a rule, is in the range from 0.01:1 to 0.1:1.

Titanium zeolites, in particular, the crystal structure of the MFI type, and the possibility of obtaining them are described, for example, in applications WO 98/55228, WO 98/03394, WO 98/03395, EP-A 0311983 or EP-A 0405978.

Titanium zeolites with structure type MFI known fact that they can be identified by their specific charts of x-ray diffraction, as well as additional bands of structural vibrations of the lattice in the range of IR at around 960 cm-1and these differ from alkali metal titanates or crystalline and amorphous phases of TiO2.

It should be called containing titanium, germanium, tellurium, vanadium, chromium, niobium, zirconium zeolites with pentasil-zeolite structure, in particular, the types rentgenograficheskim allocation to ABW-, ACO-, AEI-, AEL-, AEN-, AET-, AFG-, AFI, AFN-, AFO-, AFR-, AFS, AFT, AFX-, AFY-, AHT-, ANA-, APC-, APD-AST-, ATN-ATO-, ATS-, ATT, ATV, AWO-, AWW-, BEA, BIK-, FIFTH-, BPH-, BRE-, CAN-, CAS-, CFI, CGF-CGS-, SLEEP-, CHI-, CLO-, CON-, CZP-, DAC, DDR, DFO-, DFT, DOH-DON-TECHNOLOGICAL, EDI, EMT-, EPI-, ERI-, ESV-, EUO-, FAU-, FER-, GIS, GME-, GOO-, HEU-, IFR-, ISV, ITE, JBW-, KFI-, LAU-A, LEV-, LIO-, LOS, LOV-, LTA-, LT-, LTN-, MAZ-, MEI-, MEL-, MER-A, MER, MFI-, MFS-, MON-, MOR-, MSO-, MTF-, MTN-, MTT, MTW-, MWW-, NAT, NES, NON, OFF, OSI, PAR, PAU-, PHI-, RHO-, R-, RSN-, RTE, RTH-, RUT-, SAO, SAT, SBE-, SBS, SBT-, SFF, SGT, -, SOD-, STF-, STI, STT-, TER-, THO-, TON-, TSC-, VET, VFI-, VNI-, VSV-WIE-, WEN-, YUG-, ZON-structures, and to mixed structures of two or more nasanightlaunch. Possible for use in the method according to the invention containing titanium zeolite with structure of ITQ-4, SSZ-24, TTM-1, UTD-1, CIT-1 or CIT-5. As other containing titanium zeolite should lead zeolites with structure of ZSM-48 or ZSM-12.

In the framework of the present invention is preferably used containing titanium zeolites with MFI structure-, MEL -, or a mixed structure of MFI/ME. Then you can call the catalysts containing titanium zeolites, which in General are referred to as "TS-1, TS-2, TS-3", and also containing titanium zeolite with an isomorphic structure, such β-zeolite.

In accordance with this present invention relates also to the method described above and characterized in that the catalyst used was SILIKAL titanium with the structure of TS-1.

As solvents used in epoxydecane fit all known to the person skilled in the art solvents. Preferably organic solvents, such as alcohols, separately or in mixture of two or more. Suitable mixtures of alcohols with water. Preferably, in the framework of the present invention as a solvent for epoxidation used methanol.

When the epoxidation reaction according to the invention is formed the reaction mixture, which contains among other things α-hydroperoxidase. This mixture restore this α -hydroperoxidase restore the corresponding glycols (1,2-diols), so preventing the formation of the above-described primary, respectively, of the secondary by-products due to non-specific degradation, which causes the further processing of the reaction mixture above problems. Thus, further processing of the reaction mixture is carried out without interference and with reduced compared with the prior art equipment costs.

Recovery can be applied to all known from the literature reductants. We prefer that can be applied in water-methanol solution. The reducing agents can be used individually or in mixture of two or more reducing agents.

Below are given as examples of suitable for the purpose of the invention, reducing agents and methods of recovery. Can get all the well-known expert in the field conditions of the restoration. The selected recovery method can be carried out continuously or periodically.

For example, it is possible to recover containing α-hydroperoxidase the reaction mixture with the use of phosphorus compounds(III), such as PCl3Fofana (for example, triphenylphosphine, tributylphosphine), phosphoric acid, its salt or lipofectin is the atrium (NaH 2PO2).

Also restorative interaction with sulfur compounds(II), for example, such as H2S or their salts, polysulfides of sodium (Na2Sxx>1), dimethyl sulfide, tetrahydrothiophene, bis-(hydroxyethyl)sulfide or sodium thiosulfate (Na2S2O3), and sulfur(IV), for example, such as sulphurous acid (H2SO3) and its salts, sodium bisulfite (Na2S2O5) or S-oxide, thiourea, lead to the desired result, recovery α-hydroperoxidase in the corresponding glycols.

Next α-hydroperoxides can be restored through the interaction of the containing reaction mixture with nitrites or isoamylamine or interaction with α-hydroxycarbonyl compounds, for example with hydroxyacetone, dihydroxyacetone, 2-hydroxycyclohexanone (Glycerinum), 2-hydroxycyclohexanone (dipoena), glucose, and other able to recover sugar from the corresponding glycols.

As possible reducing agents may also be applied angioli, such as ascorbic acid or compounds that contain the link-N, for example sodium borohydride or Lamborgini sodium.

Preferably, in the framework of the present invention to recover containing α-GI is reproximity the reaction mixture is applied a method of catalytic hydrogenation.

In accordance with this present invention relates to a method of epoxidation of the above type, which is characterized in that at least one reducing agent is at least one compound which is suitable for catalytic hydrogenation.

This connection is represented by, for example, hydrogen in the presence of a suitable hydrogenation catalyst.

In the framework of the present invention under catalytic hydrogenation should involve interaction containing α-hydroperoxidase the reaction mixture with hydrogen in the presence of a suitable hydrogenation catalyst.

This catalytic hydrogenation can be both homogeneous and heterogeneous. In the framework of the present invention the catalytic hydrogenation carried out preferably in the presence of a heterogeneous catalyst.

The hydrogenation catalyst is at least one active metal VIIb-, eighth-, Ia-and Ib-subgroups of the Periodic system of the elements, either separately or in mixture of two or more.

In the framework of the present invention when it is used palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium (Os), iron (Fe), cobalt (Co), Nickel (Mi), copper (Cu), preferably Pd, Pt, Rh, Ru and Ir, particularly preferably Pd.

They can also be applied in powder form. Powder asset is on metal can be obtained by different methods. Conventional methods are, for example, thermal decomposition of salts of the active metal, the recovery of the aqueous or anhydrous solutions of salts of the active metal, for example, hydrazine, formaldehyde, hydrogen or another reducing agent. The active metal powders may contain at least one active metal or a mixture of two or more active metals.

Also for the hydrogenation can be used molded product of the active metal. Thus find application film, wire mesh (woven, knitted, and knitted patterns), granular material or crystallity powder obtained from at least one active metal or a mixture of two or more such materials.

Next to the catalytic hydrogenation can also be used and the oxides of active metals, for example, as a suspension, at least one active metal or a mixture of two or more.

In the framework of the present invention is preferably used hydrogenation catalysts, which are a combination of at least one active metal or a mixture of two or more of these metals and at least one carrier.

The content of the active metals is if we are talking about such an active metal, such as Pd, Pt, Rh, Ir, Ru and Os, typically in the range from 0.01 to 10 wt.%. If AK is positive metal selected from the group including Fe, Co, Ni, and Cu, the content usually ranges from 1 to 80 wt.%.

As the carrier may apply all known to the person skilled in the art materials that are appropriate for the purpose of applying thermal stability. So, for example, porous oxides, such as alumina, silica, aluminosilicates, zeolites, titanium oxide, zirconium oxide, chromium oxide, zinc oxide, magnesium oxide, oxides of rare earth metals, as well as active carbon or a mixture of two or more are suitable for the connection. Next can be described in the application EP 0827944 A1 types of media.

Derived from at least one active metal or a mixture of two or more active metal and at least one carrier composition, the so-called catalysts on a carrier, can be obtained by any known specialist way.

For example, such catalysts on a carrier can be obtained in such a way that at least one carrier is impregnated with a solution of at least one active metal or a mixture of two or more active metals, with several active metals can be added simultaneously or sequentially. It is also possible to impregnate the carrier with a solution fully or only partially.

Needless RA is ulitsa, the solutions of the corresponding active metals can be aprecciate media known methods, respectively, to cause evaporation or apply active metals on a carrier by electrochemical deposition. Applying at least one active metal or a mixture of two or more active metals can be described in the application EP 0827944 A1.

In both methods, the desired load carrier active metal is determined each time the desired concentration of the solution of the active metal.

Thus obtained a special pre-catalysts may contain at least one active metal or a mixture of two or more active metals radially uniformly distributed or enriched in the shell. Under the shell should be understood in the present case, the external radial plot of pre-catalyst (carrier), which has an active metal in a higher concentration compared to other sites pre-catalyst (carrier).

After impregnation or sprayed can follow other stages, such as stage of drying and/or heat treatment, as well as the stage of calcination.

Catalysts on the media in General can be obtained also in such a way that at least one preliminary stage AK the active metal precipitated in the presence of at least one suitable material carrier in alkaline or reducing conditions. Thus obtained pre-catalysts can be provided in usable form, for example in the form of bundles or granules. Then can be in General a later stage, such as drying, heat treatment and calcination.

As a pre-stage suitable in principle, all water-soluble compounds of the active metals. Examples are water soluble salts or complex salts of active metals, such as nitrates, nitrosylated, chloride, acetate, formate, or sulfates, as well as chloromethylated.

The dried pre-catalyst can be performed by all well-known expert in the field methods. In the framework of the present invention, the drying is carried out at a temperature in the range from 80 to 150°S, particularly preferably in the range from 80 to 120°C.

The preliminary calcination of the catalysts may be carried out by all known to the person skilled in the art methods. In the framework of the present invention obtained preliminary catalyst is exposed to a gas stream at a temperature preferably in the range from 150 to 500°S, particularly preferably in the range from 200 to 450°s, and the gas on the OK contains air or nitrogen.

As a rule, at the end of the process, the calcination may be carried out activating the thus obtained pre-catalyst.

The activation may be carried out by all known to the person skilled in the art methods, in which the pre-catalyst is exposed to reducing atmosphere, for example, containing hydrogen atmosphere at, if necessary, high temperature.

In the framework of the present invention prior catalysts, which contain an active metal selected from the group comprising Pd, Pt, Rh, Ir, Ru and Os, can be treated with hydrogen at a temperature of from 80 to 250°C, preferably from 80 to 180°C. Pre-catalysts, which contain an active metal selected from the group including Fe, Co, Ni, and Cu, are treated with hydrogen at a temperature of from 150 to 500°S, particularly preferably from 200 to 450°C.

The duration of treatment with hydrogen at elevated temperature depends on the concentration of at least one active metal or a mixture of two or more active metals.

In the framework of the present invention, the processing time for pre-catalyst, which contains an active metal from the group comprising Pd, Pi, Rh, Ir, Ru and Os, is preferably from 0.5 to 24 hours, particularly preferably 1 to 5 hours. With prior catalysts, which contain an active metal selected from the group including Fe, Co, Mi, and Cu, the duration of the treatment with hydrogen is preferably from 12 to 120 hours, particularly preferably from 24 to 72 hours.

The loading of the catalyst with hydrogen at activation is within the framework of the invention, generally 1 to 100 l kg-1catalyst h-1preferably from 10 to 50 l kg-1catalyst h-1.

Using the above way of catalytic hydrogenation it is possible to carry out the hydrogenation of the well-known specialist way, for example, in the liquid phase in a fixed bed or in suspension, and also using the method of irrigation or in the lower part of the column. Preferably in the present invention, the hydrogenation is carried out in a fixed bed.

The limits of pressure and temperature during hydrogenation are selected in accordance with subject to hydrogenation substance or mixture of substances. In the framework of the present invention, the hydrogenation is carried out at a pressure from 1 to 100 bar abs., particularly preferably from 1 to 10 bar abs., and at a temperature of preferably from 0 to 180°S, more preferably from 25 to 120°With, in particular from 40 to 80°C.

When the hydrogenation in a fixed bed, the residence time of the liquid in terms of volume of the reactor is from 1 second (s) d is 1 hour (h), preferably from 10 seconds to 20 minutes (min), in particular from 30 seconds to 5 minutes.

In accordance with this connection, suitable for catalytic hydrogenation containing α-hydroxyperoxide the reaction mixture, which was formed under the epoxidation according to the invention is chosen from the group comprising heterogeneous catalysts, which have as the active metal is Ru, Ni, Pd, Pt, separately or in mixture of two or more suitable media.

Preferably in this case, applying such catalysts on a carrier, which is received by one of the methods mentioned above and used for the hydrogenation containing α-hydroperoxide mixture of the product.

Hydrogenation containing α-hydroperoxide mixture of the product can be done through various methods that include epoxidation according to the invention.

According to this present invention relates also to a method for epoxidation of organic compounds having at least one C-C-double bond with hydrogen peroxide in the presence of at least one catalytically active compound and at least one solvent, which is that it includes at least the following stages:

(i) organic compound with at least one C-C double bond in the presence of, at least, one of the CSOs catalytically active compounds and, at least one solvent is subjected to interaction with hydrogen peroxide with a receipt containing α-hydroperoxide mixture of the product P1;

(ii) from a mixture of P1, respectively P1', separates obtained at the stage (!) epoxide, as well as unreacted organic compound with at least one C-C double bond, and get the product mixture P2, respectively, P2', and the mixture P2, contains generated during the interaction on stage (i) as a by-product α-hydroperoxide, and the mixture P2' mostly free from α-hydroperoxidase.

(iii) P1 and/or P2 is mixed with at least one reducing agent, and α-hydroperoxide converted to corresponding glycols with a mixture of the product P1', P3 respectively.

The reaction of the interaction on stage (i) can be carried out in the reactor, preferably in working in approximately isothermally shell-and-tube reactor in which the process is conducted under pressure and without gas phase.

The resulting mixture of product P1 contains, as a rule, along with byproduct α-hydroperoxidase used solvent, water, the target epoxide, the proportion of unreacted organic compounds with at least one C-C double bond, and other by-products, such as, for example the EP, oxygen, and the products, which are formed by the addition of solvent or water to epoxide.

After this stage (i) of the method can be restored containing α-hydroperoxide mixture of product P1 at stage (iii) described above, and α-hydroperoxide converted to corresponding glycols with a mixture of the product P1'.

This stage can be omitted.

If stage (iii) is conducted immediately after the implementation stage at the conclusion of stage (i), then the product mixture P1', used in stage (ii), largely free from α-hydroperoxidase.

If stage (iii) is not connected directly to the stage (i), then the mixture of P1 contains more α-hydroperoxidase.

From a mixture of the product P1, respectively P1'on the stage (ii) to allocate the target epoxide, as well as unreacted organic compound with at least one C-C double bond. This separation occurs at the stage (ii) obtaining a mixture of the product P2, respectively P2'.

Separation can occur known to the person skilled in the art, such as distillation, precipitation, extraction, and transmission through the membrane.

In the framework of the present invention the separation is conducted preferably by distillation.

In accordance with this present invention relates further to sposobu, characterized in that the separation obtained in stage (i) of the epoxide, as well as unreacted organic compounds with at least one C-C double bond perform on stage (ii) by distillation.

Distillation separation can be carried out using well-known expert in the field of distillation apparatus. It can be nepreryvno or periodically.

To distillation containing no α-hydroperoxide mixtures of products P1' is not subject to special requirements. It can be done with common, well-known expert in the field conditions of distillation, regarding the choice of pressure, temperature, and residence time in the lower part of the distillation column.

If subjected to distillation and containing more α-hydroperoxide mixture product, such as P1, it is necessary to follow certain conditions. Distillation is carried out in such a way that it can be ensured that α-hydroperoxidase remain largely undecomposed, i.e. preferably >80%, particularly preferably >90%, and preferably completely decayed.

In accordance with this present invention relates to a method, which differs in that the distillation separation obtained in stage (i) of the epoxide, as well as unreacted the content of inorganic fillers connection with, at least one C-C double bond at the stage (ii) is conducted at a temperature below 80°measured in the lower part used for distillation apparatus, and the stay is less than 4 hours.

Preferably the residence time is less than 2 hours, particularly preferably less than 1 hour, and the temperature preferably below 75°S, especially preferably below 70°With, in the lower part of the distillation apparatus.

In General the process is conducted at a temperature that is set by distillation at a pressure below normal.

Especially preferably the process is conducted at 65°±2°in the lower part of the distillation apparatus, and when the residence time is about 2 hours.

Along with the target epoxide, as well as unreacted organic compound with at least one C-C double bond is separated also available in a mixture of P1, respectively P1', oxygen, and other low-boiling by-products, as well as a small proportion of solvent in the distillation column at the head. The bottom product of this column forms a mixture of the product P2. It consists mainly of solvent, water, unreacted hydrogen peroxide and high-boiling, as well as other by-products. The mixture P2 also contains α-hydroperoxidase.

Containing α-hydrobar kispert mixture of product P2 may, at the stage (iii) to recover from a mixture of the product P3, and α-hydroperoxidase thus converted into glycols.

From economic considerations tend to regenerate the solvent from the produced product, it is cleaned and returned to the process. In order to prevent the above problems that exist in the regeneration in the presence of α-hydroperoxidase, solvent, usually regenerate from a mixture of the product that is already restored, i.e. which has been largely free from α-hydroperoxidase.

The product mixture P2 still contains α-hydroperoxidase. In line with this, you must first expose the restoration, as described above, with a mixture of the product P3, then from a mixture of P3 to remove the solvent, to clean it up and return in the process.

The product mixture P2' already free from α-hydroperoxidase. So it is possible to directly separate the solvent and recycle it for further use.

According to this present invention relates to a method in which after stage (iii) is then contained in the product mixture, the solvent can be completely or partially removed and, if necessary, returned to the stage (i). Preferably the solution is returned to the process.

Then when restoring containing α-hydroperoxidase mixtures product prepact the tion, that, along with α-hydroperoxidase, if necessary in a mixture of the product of the residual amount of hydrogen peroxide is recovered to produce water. This reduces the danger that can arise from uncontrolled decomposition of hydrogen peroxide with the formation of oxygen.

This provides a particular advantage when the recovery stage (iii) is carried out only after the separation stage (ii).

From the point of view of economy, and with regard to the protection of the environment gives the advantage of this solution, which formed when epoxydecane by-products are useful application. In this way there is the possibility to separate generated when restoring containing α-hydroperoxide mixtures of glycols (1,2-diole) as valuable products and submit them to other processes, for example, as starting materials or solvents.

In accordance with this present invention relates to a method, characterized in that formed when restoring containing α-hydroperoxide mixture of the product glycols can be separated as valuable products.

Department of glycols can be performed by any well-known expert in the field of fashion, for example, distill what tion, extraction or transmission through the membrane.

Separated glycols find a variety of applications, for example, as starting compounds for synthesis in the field of plastics industry or in the framework of the synthesis of natural substances, and as solvents in a wide range of industrial applications.

In accordance with this present invention relates to the use of separated as valuable products of glycols in all specialist fields of application.

Preferably the method according to the invention is used for the epoxidation of propene with hydrogen peroxide in methanol solution in the presence of silicalite titanium with MFI structure with getting probenecid. This form of execution of the method according to the invention is described in more detail below.

Formed during the reaction as by-products α-hydroperoxidase are 1-hydroperoxidation-2 and 2-hydroperoxidation-1. Recovery according to the invention they can turn into propylene glycol (1,2-propandiol), which can be separated as a valuable product.

Propylene glycol can have a variety of applications. For example, as antifreeze, brake fluid, to obtain alilovic and polyester resins, as a plasticizer for vinyl resins, as a solvent for fats, mA who ate resins, waxes, dyes and the like, Propylene glycol is also used in the food industry as a solvent for dyes and aromatic substances. It is used also as a wetting agent for tobacco products and cosmetics, as well as the impregnating substances of various ointments, creams and medicines. If you separate the optically active form, it can be used as a chiral component in various organic synthesis processes.

Propylene glycol in common is a connection that is very often used as starting substances in the synthesis of other original products for the chemical industry. After esterification with the formation of simple or complex esters of one or both hydroxyl groups, it is often used as a solvent, plasticizer or thickener, and emulsifier. Also, polyprionidae propylene glycol leads to the formation of other important polymers used in industrial processes.

When one of the preferred forms of execution of the method according to the invention for the epoxidation of propene with getting probenecid propene is subjected to interaction with hydrogen peroxide in methanol in the presence of a catalyst based on TS-1 in the main reactor (mostly shell-and-tube isothermal react the re under pressure, without gas phase) (phase (i); leads to a product mixture P1). If this turns between 75 and 95% of hydrogen peroxide.

After the main reactor the resulting propylene oxide together with unreacted propene, and oxygen, as well as other low-boiling by-products and a small amount of methanol is separated in a distillation column in its head part (stage (ii); leads to the formation of a mixture of product P2, the product of the lower part of the column).

The bottom product of this column (P2) consists mainly of methanol, water and unreacted hydrogen peroxide, and high-boiling by-products. This translates into at least one of the following reactor, the so-called additional reactor. Preferably with additional reactor talking mainly about adiabatic tubular reactor in which the process is conducted under pressure and without gas phase. The product of the lower part (P2) again subjected to interaction with propene (corresponding to re-stage (i)).

At this stage, a mixture is formed of the product (P1), which mainly consists of methanol, water, propylene oxide and by-products, among others α-hydroperoxidase, such as 1-hydroperoxidation-2 and 2-hydroperoxidation-1. This product mixture also contains, as a rule, less than 0.1 wt.% narora rowasa hydrogen peroxide.

After the reaction in the secondary reactor, the mixture is processed to obtain propylene oxide and optionally propylene glycol.

Thus, on the one hand, you have the option to first restore a mixture of the product (stage (iii))to turn cause by-products (α-hydroperoxidase) in propylene glycol. Then the propylene oxide and unreacted propene may be separated by distillation (stage (ii)), followed by regeneration of the solvent, methanol, or select another valuable product of propylene glycol from the remainder of the cubic product.

On the other hand, it is possible to remove by distillation from the mixture of the product of the additional first reactor, the propylene oxide and unreacted propene in compliance with the above conditions in distillation containing α-hydroperoxidase mixtures of product (stage (ii)), and then to recover the VAT product (stage (iii)) and separated from it as the resulting propylene glycol, and solvent, namely methanol.

Then there is the possibility to combine a mixture of the product obtained after stage (iii), and mostly free from α-hydroperoxidase. From such a mixture can be then selected propylene glycol and methanol.

Needless to say, to the each of the completed stages can be carried out several times one after the other, and formed each time the product mixture is fed to the next stage connected.

If paged product additional reactor can be set more than 0.1 wt.% hydrogen peroxide, produced by distillation of CBM product (stage (ii)) may again be subjected to interaction with propene in the further reactor compliance with the above-described sequence of steps.

In the framework of the invention, the following preferred sequence of reaction stages (A):

1) organic compound with at least one double carbon-carbon bond is subjected to interaction with hydrogen peroxide stage (i) in the presence of at least one catalytically active compounds and, in lesser measure, the same solvent to obtain a mixture of the product P1 (containing α-hydroperoxidase);

2) a mixture of product P1 in stage (iii) is mixed with at least one reducing agent, and α-hydroperoxide converted into the corresponding glycols with a further mixture of the product P1' (not containing α-hydroperoxidase);

3) from the product mixture P1' on the stage (ii) is formed by the reaction of the first stage (stage (i)) epoxide, as well as unreacted organic compound with at least one C-C double bond, you get a mix about the ukta P2';

4) of a mixture of P2' can now be allocated to the above, the corresponding α-hydroperoxidase glycols, as well as the solvent.

Especially preferred is the following sequence of stages of the reaction (In):

1) organic compound with at least one double carbon-carbon bond is subjected to interaction with hydrogen peroxide stage (i) in the presence of at least one catalytically active compound and at least one solvent to obtain a mixture of the product P1 (containing α-hydroperoxidase);

2) from a mixture of P1 allocate formed by a reaction between the first stage (stage (i)) epoxide, as well as unreacted organic compound with at least one C-C double bond at the stage (ii), and get the product mixture P2;

3) a mixture of the product P2 is mixed at the stage (iii) with at least one reducing agent, and α-hydroperoxide converted into the corresponding glycols with a further mixture of the product P3 (free α-hydroperoxidase);

4) of a mixture of P3 can now stand out as described above, respective α-hydroperoxidase glycols, as well as the solvent.

The invention is explained in more detail using the following examples.

Example (B1)

The reaction of interaction of propene is with hydrogen peroxide

In a tubular reactor (length 2 m, diameter 45 mm) with cooling shroud and the pressure regulation load 620 g of the catalyst in the form of bundles based on TS-1 (obtained according to the application WO 98/55229).

Through this reactor is passed a mixture of methanol (1560 g/h), aqueous hydrogen peroxide solution (330 g/h, approx. 40 wt.% in water) and propylene (245 g/h) at a pressure of 20 bar.

The temperature of the cooling medium in the casing of the reactor is positioned so (depending on the activity of the catalyst is between 20 and 50° (C)that is discharged from the reactor product has 90% of unreacted hydrogen peroxide. The conversion rate is determined by measuring the concentration of hydrogen peroxide in paged product using titanswhat method. Discharged from the reactor product is brought to atmospheric pressure and process in a continuously operating distillation column at atmospheric pressure. The conditions of distillation is chosen so that almost the total amount of unreacted propylene and formed of propylene oxide is distilled off at the top of the column. A certain amount of methanol goes through the head of the column (approximately the same number as the number of propylene oxide). The temperature of the distillation columns in the cube is approximately 67°With, during their stay in Cuba column status is made approximately 1 hour.

In Cuba columns get a mixture with the following composition (in wt.%):

methanol (81), water (17), hydrogen peroxide (0,9), hydroperoxidation (the sum of the two isomers (0,4), 1-methoxypropanol-2 (0,3), 2-methoxypropanol-1 (0,2), propylene glycol (0,1).

Comparative example (V1)

Paged product from example B1 without further processing serves a second continuously operating distillation column which is operated at atmospheric pressure.

In this column, the mixture is divided into mainly the anhydrous methanol fraction (head product of the column) and mainly bezmetallny water fraction (head bottom product of the column). The temperature in the cube of the column is approximately 99°S, the residence time in the cube is approximately 1 hour.

Due to the high temperature in this column are decomposed as hydrogen peroxide, and α-hydroperoxidation.

Tadema from the upper part of the column, the methanol fraction contains the following mixture (wt.%):

acetaldehyde (0,1), 1,1-dimethoxyethane (0,2), methylformate (0,002).

In addition, non-condensable exhaust gas of the upper part of the column still contains significant quantities of oxygen and should inarticulate nitrogen. Thus, this stream of methanol cannot be used for the epoxidation of propylene without additional processing.

Reactors EPoX is tiravanija not decompose nor acetaldehyde, neither 1,1-dimethoxyethane or methylformate. Thus the content of acetaldehyde and 1,1-dimethoxyethane in the further implementation of the process is increased. In contrast, the content of methylformate not increased, and (due to the very similar boiling points) would become available propylene oxide as difficult detachable pollution.

The water fraction of the cube contains the following columns impurity (wt.%):

1-methoxypropanol-2 (1,5), 2-methoxypropanol-1 (1,3), propylene glycol (0,9), formic acid (0,5), formaldehyde (0.2) and hydroxyacetone (0,2). Although propylene glycol is considered as a potential valuable product, its concentration is too low to economically regenerate it from this thread.

Example (B2)

Obtained in example B1, the mixture is collected and approximately 5 kg of this mixture with hydrogen hydronaut in an autoclave at a temperature of 50°and a pressure of 10 bar up until hydrogen is no longer absorbed (about 1 hour). As the hydrogenation catalyst used catalyst containing 5 wt.% Pd on active coal (10 g).

The resulting hydrogenation product does not contain peroxides and after removal of the catalyst by filtration separated by periodic distillation at normal pressure mainly on the anhydrous methanol fraction (head product of the column) and in the main does not contain methanol aqueous fraction (CBM product columns). The temperature in the cube column is at the end of the distillation approximately 99°With the time of distillation is approximately 8 hours.

The methanol fraction in the head product of the column other than water (approximately 100 ppm) does not contain any other detectable impurities. This flow of methanol to return again in the process of epoxidation of propylene without any additional processing.

The remaining columns in the cube aqueous fraction contains the following mixture (wt.%):

1-methoxypropanol-2 (1,5), 2-methoxypropanol-1 (1,2), propylene glycol (2.5), and simple dipropylthiocarbamate ether (mixture of isomers, traces).

Were not detected in any of formic acid or formaldehyde, no hydroxyacetone.

Due to significantly higher concentrations of propylene glycol in water fraction it can stand out from it as a valuable product and to apply further economic benefits.

Thus, the examples show that the method according to the invention avoids the disadvantages which occur in the methods according to the prior art and which caused formed as by-products α-hydroperoxidase. This method is a highly effective method of epoxidation of compounds with at least one carbon-carbon double bond, in which according to izopet is of reduced compared with the prior art equipment costs can be obtained as epoxide in its pure form, and other valuable products (glycols corresponding to α-hydroperoxidase) with simultaneous regeneration of the used solvent.

1. The method of epoxidation of propene by reacting with hydrogen peroxide in the presence of at least one catalytically active compounds, including zeolite catalyst, and at least one organic solvent with the use of separation of the products, characterized in that the mixture of the product containing α-hydroperoxidation, restore using at least one reducing agent, and α-hydroperoxidation reduced to the corresponding propylene glycol.

2. The method according to claim 1, comprising at least the following stages:

(i) propene is subjected to interaction with hydrogen peroxide in the presence of at least one catalytically active compounds, including zeolite catalyst, and at least one organic solvent to obtain a mixture of the product P1, containing α-hydroperoxidation, propylene oxide and unreacted propene,

(ii) from a mixture of P1 allocate obtained in stage (i) propylene oxide and unreacted propene, and get the product mixture P2, and the mixture P2 contains generated during the reaction in stage (i) as a side is the product α -hydroperoxidation,

(iii) P2 process, at least one reducing agent, and α-hydroperoxidation converted into the corresponding propylene glycol with a mixture of the product P3.

3. The method according to claim 1, comprising at least the following stages:

(i) propene is subjected to interaction with hydrogen peroxide in the presence of at least one catalytically active compounds, including zeolite catalyst, and at least one organic solvent to obtain a mixture of the product P1, containing α-hydroperoxidation, propylene oxide and unreacted propene,

(iii) P1 process, at least one reducing agent so that α-hydroperoxidation converted into the corresponding propylene glycol with a mixture of the product P1',

(ii) from a mixture of P1' allocate obtained in stage (i) propylene oxide and unreacted propene, and get the product mixture P2'.

4. The method according to claim 2 or 3, characterized in that after the implementation of stage (iii) is contained in the corresponding product mixture P1'/P3 organic solvent is separated completely or partially and, if necessary, return to the step (i).

5. The method according to one of claim 2 to 4, characterized in that the compartment formed in stage (i) of propylene oxide, and t is the train unreacted propene carry out the distillation in stage (ii).

6. The method according to claim 5, characterized in that the distillation separation is carried out at a temperature below 80°measured in the lower part used for distillation device, and stay below 4 hours

7. The method according to any one of claims 1 to 6, characterized in that at least one organic solvent used alcohols, separately or in mixture of two or more, or a mixture thereof with water.

8. The method according to any one of claims 1 to 7, characterized in that at least one organic solvent used methanol.

9. The method according to any one of claims 1 to 8, characterized in that at least one reducing agent contains at least one compound capable of catalytic hydrogenation.

10. The method according to claim 9, characterized in that at least one reductant using hydrogen in the presence of a suitable hydrogenation catalyst.

11. The method according to claim 10, characterized in that a suitable hydrogenation catalyst selected from the group including heterogeneous catalysts that as the active metal containing Ru, Ni, Pd, Pt, alone or in mixtures of two or more suitable media.

12. The method according to claim 10, characterized in that a suitable hydrogenation catalyst selected from the group including heterogeneous catalysts that quality is the firmness of the active metal containing Pd, Co, Pt, alone or in mixtures of two or more suitable media.

13. The method according to one of claims 1 to 12, characterized in that propylene glycol is obtained by recovering the mixture of the product containing α-hydroperoxidation, separated as an additional valuable product.

14. The method according to one of claims 1 to 13, characterized in that the zeolite catalyst used containing titanium zeolites with MFI structure-, MEL -, or a mixed structure of MFI/MEL.

15. The method according to one of claims 1 to 14, characterized in that the propene epoxidized hydrogen peroxide with getting probenecida in a methanol solvent in the presence of silicalite (zeolite) titanium with the MFI structure.



 

Same patents:

FIELD: organic chemistry, chemistry of terpene compounds.

SUBSTANCE: invention relates to a method for synthesis of 2,10-epoxypinane (β-pinene epoxide). Method involves epoxidation of β-pinene double bond with diluted hydrogen peroxide in an aqueous solution of polar solvents (methanol, N,N-dimethylformamide or acetonitrile) under condition of catalytic effect of manganese sulfate in the presence of sodium hydrocarbonate and salicylic acid. Then epoxide and β-pinene are extracted with aliphatic solvent from the reaction mixture. Polar and aliphatic solvents can be used repeatedly. At final step 2,10-epoxypinane is isolated from crude epoxide by distillation under vacuum with purity degree 95% and the yield 60-70%. Invention provides the development of technological method for synthesis of intermediate compound used in preparing some medicinal, technical and perfume preparations.

EFFECT: improved method of synthesis.

7 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 a method for the epoxidation reaction of olefin. Method involves interaction of the parent olefin-containing raw, oxygen and an agent modifying reaction in the presence of a silver-base catalyst. Agent modifying the reaction presents in the relative amount Q that represents the ratio of effective molar amount of active parts of reaction modifying agent presenting in the parent raw to the effective molar amount of hydrocarbons presenting in the parent raw. Proposed method involves the following steps: interaction in the first stage of process wherein Q values are equal to Q1 and the following interaction in the second step of process wherein the composition of the parent raw differs from composition of the parent raw used in the first step of process and Q value is equal to Q2 wherein value Q2/Q1 = 0.5-1.5. Also, invention relates to a method for synthesis of 1,2-diol or 1,2-diol ether, system for realization of method, the end product and a computer system suitable for using with proposed method.

EFFECT: improved method of synthesis.

20 cl, 2 ex

FIELD: chemical industry; production of hydrogen peroxide and oxiranes.

SUBSTANCE: the invention is dealt with a method of production of hydrogen peroxides and oxiranes. The invention provides for conductance of reaction of olefin with hydrogen peroxide at the presence of a catalyst and organic thinner. At that hydrogen peroxide is present as a water solution of hydrogen peroxide extracted mainly with the help of purified water out of a mixture produced as a result of oxidation at least of one alkylanthrahydroquinone without aftertreatment with a cleansing water and-or purification. The technical result is an increase of an output and selectivity of oxirane.

EFFECT: the invention ensures increased output and selectivity of oxirane.

17 cl, 5 tbl, 10 ex

The invention relates to a method of improving the quality of propylene oxide contaminated with poly(propylene oxide), which includes the following stages: (a) interaction of liquid propylene oxide powder of the adsorbent in an amount of from 0.05 to 15 wt.% in relation to the mass of liquid propylene oxide consisting of a silicate of magnesium and/or calcium silicate, with taking the suspension, where the average particle size of the specified powder is from 1 to 100 μm, or deletion of contaminated propylene oxide over at least one layer of the extrudates of the same adsorbent, and (b) isolation of the pure product of propylene oxide

The invention relates to a method for selection of the ethylene oxide absorption from the gas mixture obtained in the oxidation of ethylene with oxygen in the presence of silver-containing catalyst, and can be used in the production of ethylene oxide
The invention relates to a method for oxidation of hydrocarbons in the presence of a mixture of hydrogen and oxygen on the catalyst containing 0.5-10 wt.% silver and titanium containing medium, characterized in that the catalyst contains: a) a titanium containing media, such as titansilver, titanium dioxide or mixed oxides of silicon and titanium, or mixed oxides of silicon, aluminum and titanium, (b) silver particles with an average particle size of from 0.3 to 100 nm

The invention relates to a method for selection of the ethylene oxide absorption from the gas mixture obtained in the oxidation of ethylene with molecular oxygen in the presence of silver-containing catalyst, and can be used in the production of ethylene oxide

The invention relates to method the joint production of styrene and propylene oxide

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for catalytic epoxidation of propene with hydrogen peroxide in the presence of titanium-containing zeolite as a catalyst in multiphase reaction mixture comprising hydrogen peroxide-rich liquid aqueous phase containing methanol and dissolved propene and propene-rich liquid organic phase. Hydrogen peroxide is added as aqueous solution containing from 30 to 70 wt.-% of hydrogen peroxide. The reaction temperature in carrying out of the process is from 30°C to 80°C, pressure - from 5 to 50 bars, and the ratio value between propene consumption and the total consumption is in the range from 0.2 to 1. The process is carried out in tube reactor with immobile catalytic layer and fitted by a cooling agent (jacket). Invention provides enhancing degree in conversion of hydrogen peroxide and selectivity with respect to propene oxide.

EFFECT: improved method of epoxidation.

12 cl, 1 tbl, 4 ex

FIELD: organic chemistry, chemistry of terpene compounds.

SUBSTANCE: invention relates to a method for synthesis of 2,10-epoxypinane (β-pinene epoxide). Method involves epoxidation of β-pinene double bond with diluted hydrogen peroxide in an aqueous solution of polar solvents (methanol, N,N-dimethylformamide or acetonitrile) under condition of catalytic effect of manganese sulfate in the presence of sodium hydrocarbonate and salicylic acid. Then epoxide and β-pinene are extracted with aliphatic solvent from the reaction mixture. Polar and aliphatic solvents can be used repeatedly. At final step 2,10-epoxypinane is isolated from crude epoxide by distillation under vacuum with purity degree 95% and the yield 60-70%. Invention provides the development of technological method for synthesis of intermediate compound used in preparing some medicinal, technical and perfume preparations.

EFFECT: improved method of synthesis.

7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for the catalytic epoxidation reaction of (C2-C6)-olefins with hydrogen peroxide in the flow-type continuous reaction system. The reaction mixture is passed through an immobile catalytic layer with the re-flowing regimen process with at least partial removal of reaction heat formed during the reaction. The process can be carried out in the multiple reaction mixture comprising an aqueous liquid phase enriched with hydrogen peroxide containing methanol and a liquid organic phase enriched with propane. Methanol can be used as an organic solvent. Invention provides improves the conversion degree and selectivity with respect to the end product.

EFFECT: improved method of synthesis.

16 cl, 1 tbl, 6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for interaction of an organic compound with hydroperoxide. Invention describes a continuous method of interaction of organic compound comprising at least one C-C-double bond with hydroperoxide in the presence of a catalyst. Method involves interaction of organic compound at the reaction step (R1) under the range of the own pressure below 100 bars, temperature in the range 0-120°C and in the molar ratio of reacting organic compound to hydroperoxide in the range 0.7-20 with hydroperoxide in the presence of a zeolite-containing catalyst to yield at least one flow of the product (P1). Then at least one flow of the product (P1) is fed to intermediate treatment (Z1) wherein (Z1) forms at least one the hydroperoxide-containing product flow (PZ1) and wherein the intermediate treatment represents distillation separation of hydroperoxide from at least one the product flow (P1) or addition of a base to at least one the product flow (P1) and at least one the product flow is fed to at least in the reaction step (R2) wherein under pressure in the own pressure up to 100 bars, temperature in the range 0-120°C and in the molar ratio of the reacting organic compound to hydroperoxide in the range 0.7-20 hydroperoxide is subjected for interaction with an organic compound in the presence of a zeolite-containing catalyst to yield at least one the product flow (P2) wherein at least one of reaction steps (R1) and (R2) the method involves using the reactors system comprising at least two reactors joined in parallel. Also, invention describes a device for carrying out the interaction of an organic compound with hydroperoxide.

EFFECT: improved method for interaction.

9 cl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for catalytic epoxidation of (C2-C6)-olefins with hydrogen peroxide. Method is carried out in the flow-type reaction system of continuous effect wherein the reaction mixture is passed through a immobile catalytic layer inside of reactor fitted with a cooling device and in simultaneous maintaining the temperature profile into the reactor wherein the cooling medium temperature in the cooling agent is at least 40°C and the maximal temperature inside of the catalytic layer is 60°C, not above. Invention provides improving the conversion degree and selectivity of the product by using the conventional systems.

EFFECT: improved method of synthesis.

12 cl, 1 tbl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for oxidation of alkene. Method involves interaction of alkene with hydroperoxide in the presence of aluminum-free titanium-containing zeolite catalyst and the following regeneration of catalyst by a method involving thermal treatment of catalyst in the presence of hydrogen-containing gaseous flow at temperature above 120°C. Proposed method of regeneration of catalyst provides retaining mainly its initial catalytic activity and in using the stationary layer of catalyst the regeneration can be carried out without discharge of catalyst. Identical solvents can be used both for regeneration of catalyst and for carrying out the oxidation reaction and these solvents can be recirculated.

EFFECT: improved method for oxidation.

9 cl, 1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for preparing propylene oxide wherein (I) propene is subjected for conversion with hydrogen peroxide in the presence of methanol to propylene oxide to obtain a mixture (CI) containing propylene oxide, methanol, water and unreacted hydrogen peroxide; (II) from mixture (CI) mixture (CII) is removed that contains methanol, water and hydrogen peroxide to obtain mixture (Ca) containing propylene oxide; and (III) from mixture CII water is removed to obtain mixture (CIII) containing methanol and methyl formate. Invention provides enhancing yield of the end product and decreasing formation of by-side products.

EFFECT: improved preparing method.

9 cl, 1 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides process for production of propylene oxide in presence of methanol, wherein propylene oxide is separated from propylene oxide/methanol mixture and methanol-containing raw mixture is then processed. Process is characterized by that, in the course of processing, methanol is separated from mixture containing methanol and methyl formate formed in the process.

EFFECT: enhanced process efficiency.

9 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention describes a method for preparing oxirane in reactor comprising a liquid reaction medium. Method involves carrying out reaction between olefin and peroxide compound in liquid reaction medium in the presence of a solid catalyst and a solvent. Solid catalyst comprises zeolite as an active component and it is used in form of particles wherein at least part of particles present in reactor in the fluidized state. Invention provides increasing rate of the process that results to the enhanced output.

EFFECT: improved preparing method.

1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing oxirane. Method involves interaction of olefin and peroxide compound in the presence of catalyst and solvent in at least two in-line fitted reactors and each reactor comprises part of catalyst. Method is carried out for two successive epoxidation reactions with intermediate distillation. Method provides reducing formation of by-side substances.

EFFECT: improved preparing method.

10 cl, 1 dwg, 2 ex

FIELD: chemical industry; production of hydrogen peroxide and oxiranes.

SUBSTANCE: the invention is dealt with a method of production of hydrogen peroxides and oxiranes. The invention provides for conductance of reaction of olefin with hydrogen peroxide at the presence of a catalyst and organic thinner. At that hydrogen peroxide is present as a water solution of hydrogen peroxide extracted mainly with the help of purified water out of a mixture produced as a result of oxidation at least of one alkylanthrahydroquinone without aftertreatment with a cleansing water and-or purification. The technical result is an increase of an output and selectivity of oxirane.

EFFECT: the invention ensures increased output and selectivity of oxirane.

17 cl, 5 tbl, 10 ex

Up!