Method for oxidation of alkene

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

 

The present invention relates to a method of regeneration of a zeolite catalyst, and integrated way to obtain epoxide, which carry out the regeneration according to the invention.

In the prior art it is known that the catalytic activity of heterogeneous catalysts for liquid-phase oxidation of organic compounds (in this case we are talking in particular about epoxydecane organic compounds containing at least one double carbon-carbon bond, with the use of hydroperoxide in the presence of zeolite catalyst) as the flow of the experiment is reduced, so that the corresponding catalysts must be regenerated.

The prior art in various ways regeneration of zeolite catalysts. In this regard, reference should be made to international patent WO 98/55228 and references cited therein prior art, according to which there are two fundamentally different ways regeneration of catalysts.

1. If the catalyst is used in the form of a suspension, it is separated from the liquid reaction mixture and transferred to suitable for carrying out the regeneration of the device in which it is recovered by heat treatment carried out in the presence of oxygen.

2. If the catalyst is used in the form of a stationary layer of liquid fsuliwoc or pumped by the pump, and regenerate the catalyst by heat treatment carried out in the absence of oxygen or in the same reactor or in another dedicated to the regeneration device.

In addition, in accordance with the prior art have been repeatedly described the regeneration is carried out by treating the catalyst at elevated temperature liquid, which is simultaneously oxidizing agent such as hydrogen peroxide. In this regard, reference should be made to German patent application DE-A 19528220 and international patent WO 98/18555.

Taking into account the above prior art underlying the present invention, the task consisted in creating advanced, improved, in particular more efficient method for the regeneration of zeolite catalysts, which can without problems be included in a continuous and integrated method of producing epoxides type considered here, with the use of this method, in particular, is not accompanied by long periods of disconnection and idle time required for opening or closing the reactors. In particular, this method should be suitable for the regeneration of zeolite catalysts used for carrying out oxidation reactions in the stationary layer. In particular, when using the regeneration method according to the invention have the ü largely suppressed or at least, severely weakened the possibility of local overheating in the catalyst bed during regeneration, such as local overheating of the catalyst adversely affect its activity or mechanical stability for subsequent reuse in an integrated way oxidation of alkenes according to the invention.

These and other problems are solved using the method of regeneration of a zeolite catalyst according to the invention.

Thus, the present invention relates to a method of regeneration of a zeolite catalyst comprising a thermal treatment of the catalyst in the presence of a gas stream at temperatures higher than 120°S, and the gas stream contains hydrogen.

Thus preferably chosen such regeneration time, that the activity of the catalyst was able to achieve at least 85% from the corresponding initial values.

In accordance with the present invention can be regenerated as used in the form of a suspension of powdered catalysts, and molded, for example molded or extruded catalysts used in stationary layer, as well as catalysts, crystallized on the grids, for example, made of refined steel, bolted, or nozzles, and rolled atory with sheath, consisting of an inert core of SiO2that α-Al2About3, calcined at high temperature TiO2, steatite, which is covered with a shell containing the active zeolite catalyst.

If the catalyst is used in the form of a suspension, it is first necessary to isolate from the reaction solution, for example, by filtration or centrifugation, and at least partially deactivated catalyst can then be sent for regeneration. High temperature process steps in the process of regeneration of such powdered catalysts is preferably carried out in a rotary tube furnaces. If we are talking about the regeneration of the catalyst used in the form of a suspension, particularly preferred is a continuous removal of a certain part, at least partially Deaktivierung catalyst from the reaction zone, its regeneration is carried out outside of this zone in accordance with the method according to the invention, and returning the regenerated catalyst to the reaction zone.

Along with regeneration used in the form of suspensions of powdered catalysts by the method according to the invention can be regenerated also molded catalysts, for example catalysts used in the form of a stationary layer. In this case, the regeneration of PR is doctitle carried out directly in the reaction device, that is, there is no need for unloading and reloading of the catalyst, making it possible to avoid exposure to additional mechanical loads. When regeneration of the catalyst is carried out directly in the reaction device, first stop the reaction, if necessary, unload contained in the reaction mixture, regenerate the catalyst, and then continue the reaction.

According to the invention, the regeneration as a powder, and molded catalysts proceeds basically in the same way.

The method according to the invention is suitable in particular for the regeneration of the stationary layers of catalysts loaded, in particular, in a tube or shell-and-tube reactor. While the terms "tubular reactor" and "shell-and-tube reactor" refers to a set of parallel spaced channels in the form of tubes, which can have arbitrary cross-section. The mutual spatial arrangement of the tubes firmly fixed, and the tube is preferably located at a certain distance from each other and preferably all of them surrounded by a common jacket. Thus, through the shirt can be skipped, for example, heating or cooling agent, thanks to all the tubes is the same temperature.

In addition, predpochtitelnei is the length of the individual tubes, inside preferably used tube or shell-and-tube reactor, at approximately from 0.5 to 15 m, preferably from 5 to 15 m and, in particular, from 8 to 12 PM

Regenerated catalyst preferably should remain in the reactor. The regeneration method according to the invention can also be used for the regeneration of zeolite catalysts in several reactors connected in parallel or in series, or in reactors, some of which are connected in parallel, and the other series.

The regeneration according to the invention is carried out at temperatures higher than 120°S, preferably greater than 350°and, in particular, in the interval from 400 to 650°C.

Regards used for the regeneration gases, there are no fundamental limitation exists if the following conditions are met: the regeneration can be carried out so that the inside of the reactor the catalyst is not heated, for example, as a result of combustion located on its surface organic deposits that can damage the porous structure and/or to the reactor, and to prevent the formation of explosive mixtures, and also provided that the composition of the regeneration gas is hydrogen. The regeneration is preferably carried out so the m way to ensure that the temperature in the zone of local overheating occurring within the catalyst layer, is increased by no more than 10-20°S, preferably not more than 20°C.

In a particularly preferred embodiment of the present invention, the regeneration gas is hydrogen, or a mixture of carbon dioxide and hydrogen, if necessary, respectively, with the addition of carbon monoxide. The content of hydrogen or a mixture of carbon dioxide with hydrogen in the regeneration gas in the regeneration of the catalyst is from 0.1 to 100% vol., preferably from 0.5 to 20% vol. and more preferably from 1 to 5% vol.

In addition, the composition of the regeneration gas may include inert gases such as nitrogen, noble gases such as argon or helium, hydrocarbons, such as methane or ethane, and natural gas.

Relatively regenerated in accordance with the present invention zeolite catalysts there are no special restrictions.

Zeolites, as you know, are crystalline aluminosilicates with ordered channel and cage structures and the size of the micropores is preferably less than 0.9 nm. The mesh structure of zeolites formed by tetrahedronsandUnited General oxygen bridges. Browse famous structurelite presents, for example, W.M. Meier, D.H. Olson and Ch. Baerlocher, Atlas of Zeolithe Types", Elsevier, 4. Aufl., London 1996.

Also known zeolites that do not contain aluminum, and the silicon Si(IV) in the crystal lattice silicate is partly titanium as Ti(IV). Such titanium containing zeolites, in particular, having a crystal structure of the MFI type, and the possibility of obtaining them are described, for example, in European patent applications EP-A 0311983 and EP-A 405978. These materials, along with silicon and titanium may also contain additional elements, in particular, aluminum, zirconium, tin, iron, cobalt, Nickel, gallium, boron or a small amount of fluorine. In zeolite catalysts, preferably regenerated by the method according to the invention, the titanium may be partially or completely replaced by vanadium, zirconium, chromium or niobium or a mixture of two or more of these elements. The molar ratio of the content of titanium and/or vanadium, zirconium, chromium or niobium to the total content of silicon, titanium and/or vanadium, zirconium, chromium and/or niobium, as a rule, is in the range from 0.01:1 to 0.1:1.

Titanium containing zeolites, in particular, having a crystal structure of the MFI type, and possible methods for their preparation are described, for example, in international patent applications WO 98/55228, WO98/03394, WO 98/03395 and European patent applications EP-A 0311983, EP-A 405978, it is suitable the contents of which are fully incorporated in the context of this application.

About titanium containing zeolites having the crystal structure of the MFI, it is known that they can be identified by a particular model for recognition of the respective images of x-ray diffraction and an additional band of skeletal vibrations at 960 cm-1the infrared region, and these identification characteristics distinguish them from alkali metal titanates or crystalline and amorphous phases of titanium dioxide TiO2.

In particular, there are titanium-, germanium-, tellurium-, vanadium-, chromium-, niobium -, circumistances zeolites having the crystal structure of the zeolite pentasil, in particular, the types with rentgenograficheski identified crystal structure ABW, ACO, ABI, 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, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS, SLEEP, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, EUO, FAU, FER, GIS, GME, GOO, HEU, IFR, ISV, ITE, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, MAZ, MEI, MEL, MER, MER, MFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAT, NES, NON, OFF, OSI, PAR, PAU, PHI, RHO, RON, 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, and mixed structures consisting of two or more of the above crystal structures. In addition, in the method according to the invention can be used titanium containing zeolites having the crystal structure of ITQ-4, SZ-24, TTM-1, UTD-1, CIT-1 or CIT-5, Other possible titanium containing zeolites are materials with a crystalline structure of ZSM-48 or ZSM-12.

Especially preferred for use in the method according to the invention are titanium containing zeolites having the crystal structures of MFI, MEL, or a mixed structure of MFI/MEL. Other preferred catalysts are, in particular, titanium containing zeolites, in General referred to as TS-1, TS-2 and TS-3", as well as titanium containing zeolites having relatively isomorphic β-zeolite crystal structure.

Thus, the present invention concerns also the above method, characterized in that the catalyst is titanosilicates, having crystal structure of TS-1.

Under used in accordance with the present invention alkenes " means any compound containing at least one double carbon-carbon bond.

Examples containing at least one double carbon-carbon bond of the organic compounds are the following alkenes:

Aten, propene, 1-butene, 2-butene, isobutene, butadiene, pentene, piperylene, hexene, hexadiene, heptane, octane, Diisobutyl, trimethylpentane, nonini, dodecan, tridecen, alkenes from tetracosane to Aksenov, polybutadienes, polyisobutene from the prégny, terpenes, geraniol, linalool, linalyl-acetate, metalinsulator, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxy, vinylcyclohexane, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, inden, tetrahydroindene, methylsterol, Dicyclopentadiene, divinylbenzene, cyclododecene, cyclododecatriene, stilbene, diphenylbutadiyne, vitamin a, betacarotene, vinylidenefluoride, allylchloride, Cotillard, metallicgold, dichlorobutene, allyl alcohol, metalloy alcohol, butanol, butanediol, cyclopentanediol, pentanol, octadienal, tridecanol, unsaturated steroids, ataxite, isoeugenol, anethole, unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, feniluksousna acid, unsaturated fatty acids, e.g. oleic acid, linoleic acid, palmitic acid, fats and oils of natural origin.

In the method according to the invention is preferably used alkenes with 2 to 8 carbon atoms. Especially preferred is the use of Athena, propene and butene. Preferred, in particular, is the use of propene.

Thus, the present invention relates also to the above method or the above integrated method, characterized in that as alce is and use propene.

Under hydroperoxides imply any hydroperoxides, including hydrogen peroxide, and relatively used in the method according to the invention, solutions of hydroperoxides and their receipt reference should be made to the relevant prior art, for example, in German patent application DE 19723950.1 and quoted in her art.

To get used hydrogen peroxide, for example, to use antrahinonovye way through which synthesize almost all the quantity produced in the world of hydrogen peroxide. This method is based on the catalytic hydrogenation of a derivative of anthraquinone to the corresponding anthrahydroquinone, the interaction of the latter with oxygen, leading to the formation of hydrogen peroxide, and subsequent allocation of peroxide formed by extraction. The cycle of catalysis completed re-hydrogenation regenerated derivative of anthraquinone.

Description antrahinonovye method described in "Ullmanns Encyclopedia of Industrial Chemistry", 5th. Edition, Band 13, Seiten 447-456.

In addition, to obtain hydrogen peroxide can be converted sulfuric acid in peroxidizing sulfuric acid by anodic oxidation with simultaneous cathodic hydrogen evolution. Subsequent hydrolysis peroksidaznoi sulfuric acid leads to the formation of peroxone the Oh of the acid, which is then converted into hydrogen peroxide and sulfuric acid, is returned to the initial stage of synthesis.

Hydrogen peroxide, of course, it is possible to synthesize and of its component elements.

Before using hydrogen peroxide in the method according to the invention it is possible to remove unwanted ions, such as those contained in the implemented trading network of the peroxide solution, which, along with other suitable methods are described, for example, in international patent application WO 98/54086, German patent application DE-A 4222109 or international patent application WO 92/06918. In addition, at least one salt contained in the hydrogen peroxide solution may be removed from this solution by ion exchange in the device, characterized in that it is provided with at least one sour ion exchange layer with a screening 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 accordance with the present invention in principle can be used any sour layers of cation and/or anion exchange resins. However, the ion-exchange layer can be formed by a mixture of cation and anion exchange resin, there can be used a so-called mixed ion-exchange layers. In accordance with one preferred embodiment altoadige of the invention use only one type of sour ion-exchange substances. In another embodiment, it is preferable to use a basic ion-exchange substance, particularly preferably a basic anion exchange resin, and more preferably the anion exchange resin with weak basicity.

The present invention in one particularly preferred embodiment relates to a method of regeneration of a zeolite catalyst, comprising the following stages(1)-(4):

(1) washing of the zeolite catalyst solvent

(2) drying the washed zeolite catalyst at a temperature of from -50 to 250°C

(3) heating the dried catalyst

(4) the heated regeneration of the catalyst by the method according to the present invention.

This is the preferred method of regeneration of the zeolite catalyst preferably includes the following additional stages (5) and/or (6):

(5) cooling the regenerated on stage (4) catalyst

(6) air conditioning obtained in stage (4) or (5) of the catalyst.

Below describes each of these stages. Special attention should be paid to what is under be the regeneration of a zeolite catalyst, as a rule, imply the catalyst used in the oxidation of alkene by its interaction with a hydroperoxide, preferably carried out in a continuous manner, and which is due to the reduction of its catalytic active the tee should be subjected to regeneration. However, as emphasized above, the regeneration of the catalyst according to the invention is preferably carried out in the same reactor (reactors), in which (whom) interact alkene with a hydroperoxide in the presence of the subject catalyst regeneration.

Another, particularly preferred implementation of the present invention provides for operation of the reactor, combined with the allocation of securities of the target product and catalyst regeneration method according to the invention, since this technology allows recirculation of the solvent in a closed loop.

(1) Washing of the zeolite catalyst solvent

The first stage of this variant regeneration according to the invention includes, mainly, washing Deaktivierung catalyst solvent, which, first of all, stop filing the initial reagents, i.e. hydroperoxide and organic compounds. The solvent may be used any compound capable of well dissolving the product of oxidation of alkene.

Such solvents are preferably chosen from the group comprising water, an alcohol, preferably methanol, aldehyde, acid, in particular formic acid, acetic acid or propionic acid, a nitrile, a hydrocarbon, halogenated hydrocarbon. More p is the fractional information, concerning such solvents described in the international patent application WO 98/55228, the relevant contents of which are fully incorporated in the context of this application.

Preferred solvents are compounds used as solvents during the implementation stage of the reaction, for example, at the stage epoxidation of olefin in the presence of the subject to recovery of the catalyst. The solvents used, for example, when epoxydecane olefins include water, alcohols, in particular methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, allyl alcohol or ethylene glycol, ketones, in particular acetone, 2-butanone, 2-methyl-3-butanone, 2-pentanone, 3-pentanone, 2-methyl-4-pentanone or cyclohexanone.

When washing use the same solvent for the reaction, washing the catalyst to continue the flow of the solvent at a temperature in the General case component is from 40 to 200°With, if necessary, at elevated temperature and under pressure. Leaching of the catalyst is preferably continued until until the contents of the reaction product in the reaction mixture is less than 1% of the initial value. If leaching of the catalyst is carried out in a solvent which is different from that used in the reaction, then stop innings of the initial reagents (hydroperoxide, organic compounds) used in the reaction solvent and proceed to the flow of solvent designed for cleaning. Especially preferred is the use of the same solvent as for the reaction and leaching of the catalyst.

As for the duration of the washing process, there is no limitation in this respect is not there, and preferred is a longer leaching period, and, therefore, perhaps more complete removal of the reaction product and organic deposits.

(2) Drying the washed zeolite catalyst at a temperature of from -50 to 250°

Upon completion of the washing of the catalyst used, the solvent is drained from the reactor or pumped by the pump. The porous catalyst continues to hold a significant amount of solvent, the bulk of which is removed by drying in a gas stream at a temperature of from -50 to 250°C, the drying temperature is near the boiling point of the solvent at a corresponding selected pressure. Typical drying temperature is 50°above or below the boiling point of the solvent.

In the General case, for drying an inert gas, such as nitrogen, argon, carbon dioxide, hydrogen, synthesis gas, methane, ethane or natural gas is preferably nitrogen. Gas containing RAS is veritel, eliminate as waste, for example, by burning in a flare, or directed to a suitable place, for example, in the area of separation of the reaction product obtained by the method of alkane oxidation, where the solvent contained in the gas is subjected to regeneration.

In accordance with a preferred embodiment of the present invention flushing carried out under pressure at a temperature above the boiling point of the solvent, and after draining the solvent pressure is reduced to such a level that before or during the feed gas for drying the catalyst portion of the solvent could evaporate due to the latent heat of the reactor.

For drying of the catalyst can be used as the warmth of the injected gas, and heat the liquid, for example, in the jacket of the tubular reactor. If drying is carried out at a temperature below 150°preferred is the use of heat of liquid, when the drying temperature in excess of 150°With, preferably using gas heat.

(3) heating the dried catalyst

After drying shall be heated catalyst regeneration, which may use any known in the art methods, and the catalyst is heated preferably in the presence of a flow of inert gas, particularly nitrogen, carbon dioxide, argon, methane is, ethane or natural gas.

In accordance with a special form of the method according to the invention the catalyst is in the tubes of the shell-and-tube reactor. In reactors of this type of heat in the system is transmitted through the shirt, and the heating rate should be selected in such a way as to avoid unacceptably high mechanical stresses in the reactor. A typical heating rate is from 0.01 to 0.2°C/min

(4) the heated Regeneration of the catalyst by the method according to the present invention

After drying of the catalyst involved in its regeneration using is described in detail in this application method.

(5) Cooling the regenerated on stage (4) catalyst

Upon completion of regeneration of the catalyst according to stage (4) preferably the entire reactor together with inside it the regenerated catalyst is cooled to a temperature preferably below 200°C.

(6) air Conditioning obtained in stage (4) or (5) catalyst

After regeneration according to the invention or cooling, the catalyst may optionally be subjected to conditioning for a controlled way to take the heat of absorption of the solvent or product extraction before reuse of the catalyst. With this purpose, an inert gas) is t with a small amount of solvent, preferably similar to that used in the reaction or for washing of the catalyst, in particular, with alcohol, such as methanol, and a stream of inert gas containing a specified vaporous solvent is passed through the catalyst bed. The solvent content and the volumetric feed rate of the conditioning gas filled in a way that has not occurred invalid maximum temperature rise of the catalyst. The temperature preferably should not be more than 100°to exceed the average temperature of the heat exchanger, for example, the temperature inside the jacket of the tubular reactor.

After the decay heat stop filing solvent conditioning gas, and the reactor, which preferably use a reactor with a fixed bed of catalyst, fill with fluid and put into operation.

When carrying out the optional steps (5) and (6) the method according to the invention, it is important not too fast to cool and condense loaded in the reactor the catalyst that can be a negative impact. However, for the same reasons, you should avoid too rapid increase of the temperature inside the catalyst layer in air-conditioning.

As reported above, the regenerated catalyst is preferably again use the La collaboration alkene with the hydroperoxide. In particular, the regeneration according to the invention or an integrated method of oxidation of the alkene can preferably be used for the conversion of propylene to propylene oxide by means of hydrogen peroxide, more preferably carried out in a solution of methanol.

The method according to the invention has in particular the following advantages.

- Through the use of gentle reaction conditions zeolite catalysts could be regenerated in such a way that they basically retain the original catalytic activity.

- When using a stationary layer of catalyst regeneration method according to the invention can be carried out without unloading of the catalyst from the reactor.

In accordance with the method according to the invention for the regeneration of the catalyst, and for the implementation of the reaction can be used the same solvents that can be fully recycled.

The invention can be illustrated by the following example.

Example

Used in the form of a stationary layer heterogeneous catalyst for the epoxidation of propene to propylene oxide (60 wt%. titanium containing zeolite TS-1 and 40% of the mass. silica as a binder) were discharged from the tubular reactor after which lasted for 850 hours of operation. According to the results of helices is on analysis of the carbon content in the discharged catalyst was 1.2% of the mass. According to the results of standard testing the activity of the catalyst according to the German patent application DE 19859561.1, example 10, the content of propylene oxide formed in the presence of the unloaded catalyst was 3.6% of the mass.

800 g unloaded catalyst was placed in a tubular reactor (tube length 2000 mm, inner diameter 40 mm)was heated for 2 hours in a stream of nitrogen (900 l/HR) and hydrogen (100 l/h) to a temperature of 450°With, was kept under these conditions for 6 hours and then cooled. The reactor was not observed any dissipation.

The residual carbon content of the regenerated catalyst was 0.1% of the mass. According to the above standard test the activity of the catalyst, the content of propylene oxide formed in the presence of the regenerated catalyst was 4.9% of the mass.

1. The method of oxidation of alkene, including interaction alkene with a hydroperoxide in the presence of titanium-containing zeolite catalyst, free of aluminum, and the subsequent regeneration of the catalyst by the method consisting in the heat treatment of the catalyst in the presence of a gas stream at temperatures above 120°S, and the gas stream contains hydrogen.

2. The method according to claim 1, and the gas stream along with hydrogen gas contains carbon dioxide and/or the monoxide of plastics technology : turning & is Yes.

3. The method according to claim 1 or 2, with the zeolite catalyst is titanosilicate with the crystal structure of the MFI.

4. The method according to one of claims 1 to 3, and regenerative carried out in a reactor with a stationary layer.

5. The method according to claim 4, and a reactor with a stationary layer is tubular or shell-and-tube reactor.

6. The method according to one of claims 1 to 5, comprising the following stages:

(1) washing of the zeolite catalyst solvent

(2) drying the washed zeolite catalyst at a temperature of from -50 to 250°C

(3) heating the dried catalyst

(4) the heated regeneration of the catalyst by the method according to one of claims 1 to 5.

7. The method according to claim 6 comprising additionally at least one of the following stages (5) and (6), which is carried out after the stage (4):

(5) cooling the regenerated on stage (4) catalyst

(6) air conditioning obtained in stage (4) or (5) catalyst

and supplied to the catalyst inert gas mixed with a small amount of solvent, and the flow of inert gas containing vapors of the solvent, is passed through the catalyst bed.

8. The method according to one of claims 1 to 7, and the regenerated catalyst is again used in the interaction alkene with hydroperoxide.

9. The method of claim 8, and as alkene use p is open, and the hydroperoxide is hydrogen peroxide.



 

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The invention relates to a method for epoxidation prehiring of olefin, which includes the interaction prehiring of the olefin with oxygen source in the presence of salt catalyst

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to regeneration of silica powder-containing catalysts with SiO2/Al2O3 ratio at least 12, which are deactivated by coking occurring during aliphatic hydrocarbon dehydrocyclodemerization reaction. Regeneration process comprises preliminary nitrogen purge of reactor system to remove hydrocarbons until their content drops below 0.5%, treatment of catalyst at 300-550°C and pressure 0.1-2.0 MPa with catalyst-regeneration gas in the form of nitrogen-oxygen mixture pumped through closed regeneration circuit, withdrawal of a part of combustion products and moisture formed during coke combustion reaction, wherein regeneration gas loss is continuously recompensed to maintain specified working thermobaric conditions in the regeneration circuit. Simultaneously, oxygen content in regeneration gas is stepwise raised from 0.1 to 21 mol % followed by ageing of catalyst under each step conditions. Regeneration gas utilized is emission gases from process furnaces used to preheat feed for various chemical processes and operated with the main-pipeline natural gas, which emission gases are processed in mixture with said main-pipeline natural gas in flow-type reactor on metal block catalyst, wherein concentration of natural gas (methane) in mixture with emission gases should be 2.75, 2.4, and 0.5 vol % for three regeneration gas compositions used in regeneration cycle, which, at regeneration gas intake 40 m3/h used to replenish process flowsheet, will require consumption of natural gas for preliminary treatment of emission gases on metal block catalyst prior to being fed into regeneration circuit 1.1, 0.96, and 0.2 m3/h, respectively.

EFFECT: reduced power consumption due to eliminated use of pure nitrogen in catalyst regeneration stage.

1 tbl, 3 ex

The invention relates to the regeneration of catalysts containing zeolite type pentasil, deactivated as the result of kokoulina when carrying out the reaction of dehydrocyclization aliphatic hydrocarbons

The invention relates to the field of chemistry, in particular to the regeneration of catalysts containing zeolite type pentasil, deactivated as the result of kokoulina when carrying out the reaction of dehydrocyclization aliphatic hydrocarbons

The invention relates to the refining, in particular to a method of oxidative regeneration of spent catalyst in the catalytic cracking of crude oil

The invention relates to methods of oxidizing regeneration superagency catalysts, sorbents and molecular sieves, i.e

The invention relates to catalytic processes in petroleum refining and petrochemical industries and can be used to increase the efficiency of the pre-regeneration aluminosilicate cracking catalyst

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to regeneration of silica powder-containing catalysts with SiO2/Al2O3 ratio at least 12, which are deactivated by coking occurring during aliphatic hydrocarbon dehydrocyclodemerization reaction. Regeneration process comprises preliminary nitrogen purge of reactor system to remove hydrocarbons until their content drops below 0.5%, treatment of catalyst at 300-550°C and pressure 0.1-2.0 MPa with catalyst-regeneration gas in the form of nitrogen-oxygen mixture pumped through closed regeneration circuit, withdrawal of a part of combustion products and moisture formed during coke combustion reaction, wherein regeneration gas loss is continuously recompensed to maintain specified working thermobaric conditions in the regeneration circuit. Simultaneously, oxygen content in regeneration gas is stepwise raised from 0.1 to 21 mol % followed by ageing of catalyst under each step conditions. Regeneration gas utilized is emission gases from process furnaces used to preheat feed for various chemical processes and operated with the main-pipeline natural gas, which emission gases are processed in mixture with said main-pipeline natural gas in flow-type reactor on metal block catalyst, wherein concentration of natural gas (methane) in mixture with emission gases should be 2.75, 2.4, and 0.5 vol % for three regeneration gas compositions used in regeneration cycle, which, at regeneration gas intake 40 m3/h used to replenish process flowsheet, will require consumption of natural gas for preliminary treatment of emission gases on metal block catalyst prior to being fed into regeneration circuit 1.1, 0.96, and 0.2 m3/h, respectively.

EFFECT: reduced power consumption due to eliminated use of pure nitrogen in catalyst regeneration stage.

1 tbl, 3 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

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