The oxidation catalyst, the method of its production (options), the method of obtaining asimov, the way hydroxylation of aromatic hydrocarbons and catalytic method for the oxidation of hydrocarbons

 

(57) Abstract:

The invention relates to new catalysts for oxidation, as well as to methods for their preparation and use. These new oxidation catalysts contain crystallized in situ to the active coal or metal oxides silicalite titanium. Content silicalite titanium preferably 30 to 60 wt.%. The atomic ratio of Si/Ti deposited on the carrier phase 10 - 100. These catalysts are suitable in particular for oxidation reactions using H2O2under mild conditions, i.e. at 20 - 120oC and pressures, use them equal to or above atmospheric pressure. 6 C. and 16 h.p. f-crystals, 3 tables.

The invention relates to a new oxidation catalyst, the method of its production, as well as to the use of this catalyst for oxidation reactions under mild conditions, for example, at 20 - 120oC and pressures equal to or above atmospheric pressure.

There are many oxidation catalysts used for the oxidation reactions with H2O2as oxidant. So, paved the description of the invention to unaccepted application for patent Germany 3 309 669 describes a catalyst of the zeolite with impurity (alien) elements. As the modifier is atarov oxidation are preferably used crystalline titanium silicates. So, the following use cases: a simple synthesis glycolmonomethyl esters (European patent EP-100 118), epoxidation of monoolefins (European patent EP-100 119), epoxidation of diolefins to monoepoxides (European patent EP-190 609), the conversion of styrene-phenolaldehyde (European patent EP-102 097), hydroxylation of aromatic hydrocarbons (patent UK 2 116 974), the oxidation of alkanes to alcohols and ketones (Nature , 345 (1990), 240), oxidation of alcohols to aldehydes, accordingly ketones (European patent Ep-102 665), as well as conversion of cyclohexanone with NH3and H2O2in the oxime (European patent Ep-208 311 and EP-226 257).

To obtain crystalline titanium silicates in the literature to indicate various ways. In U.S. patent 4 410 501 describes two ways to obtain. Both methods include obtaining gel TiO2- SiO2that in the presence of tetrapropylammonium (TPAO) and water under hydrothermal conditions is transformed into a crystalline titanium silicate (TC-I). As initial products for gel formation are tetraethylorthosilicate (TEOS) and tetraethylorthosilicate (TEOT), respectively colloidal SiO2and tetrapropylammonium the>

Further, the titanium silicates can be obtained by high-temperature processing of H-ZSM-5 or silicate-1 using TiCl4(Catal. Lett. 13) (1991), 229). In the European patent EP-299 430 protected way of getting silicalite titanium, in accordance with which the amorphous SiO2impregnated compound of titanium and then in the presence of template (a Templates) crystallizes to silicate titanium. Resulting titanium silicates have little selectivity in obtaining cyclohexasiloxane. Only due to the applied activation of the catalyst with H2O2and H2SO4improved selectivity for the formation of oxime; however, the achieved selectivity is too small for use on an industrial scale.

In [1] describes ecologically unfavorable variant of the synthesis of titanium silicate using such reagents as SiO2, oxalic acid, titanium oxalate, tetrapropylammonium, ammonium fluoride and the zeolite crystallization centers, which lead to large zeolite crystals. The resulting dimensions of the zeolite crystallites 15 - 20 μm favorable for separation by sedimentation, but in many oxidation reactions field>- SiO2products in the presence of templates in silicalite titanium is protected in the European patent EP-311983.

All of these are known from the prior art catalysts based on silicalite titanium is very expensive, have unfavorable combination of easily accessible surface of the zeolite and the amount of catalyst particles and along with this they have been badly manipulated. In addition, to achieve high activity and selectivity required before using the activated using H2O2and H2SO4.

The objective of the invention is to develop cost-oxidation catalysts which have improved properties in terms of activity and selectivity.

This problem is solved thanks to a new catalytic system consisting of crystallized in situ to the active coal or metal oxide as a carrier of titanium silicate with MFI structure.

The content of titanium silicate in the proposed according to the invention the catalyst is in the range from 1 to 90 wt. % better 10 - 90 wt.%. For deposited on active carbon silicalite titanium preferred content silicalite titanium is within stafleet 30 - 50 wt.%.

The atomic ratio of Si/Ti in the deposited phase is a value ranging from 10 to 100.

As oxides, on which "recristallization" silicalite titanium, used Al2O3, SiO2, TiO2, ZrO2or Al2O3SiO2. It is also possible to use any mixtures of these oxides.

Unexpectedly found that silicalite titanium deposited on active carbon or oxide carriers, namely recristallization on these carriers in situ (hereafter referred to as "applied"), have greatly improved activity and selectivity compared to silicalite titanium without media. Moreover they also have good sedimentation properties, so that the grain size of the catalyst is equal to < 63 μm with a maximum particle size distribution in the region of 8 to 30 μm. The grain size of pure silicalite titanium in contrast, has a value of 5 μm.

The reason for this unexpected action is in the interaction between the carrier and silicalite titanium. In contrast to the pure, without media silicalite titanium appear significantly different physico-chemical properties. These are znana, as well as the shift of the Si-O-Ti-bands at 960 cm-1in the area of the smaller wave numbers.

The expression "significantly lower" means that the reduction lies outside of the limit of error of measurement for pure silicalite titanium.

According to literature data (J. of Catalysis 130, (1991), 1), unit cell volume silicalite titanium case, the atomic ratio Ti/(Ti + Si) = 0 takes the value = 5,3447 nm3and in the field of atomic ratios of Ti/(Ti + Si) from 0 to 0,091 increases linearly with increasing titanium content. When the ratio of Ti/(Ti + Si) = 0,091 the volume of the unit cell is 5,3965 nm3. Fixed on active coal, and the native metal oxides silicalite titanium detect a significant reduction in the unit cell (see table. 1), which tends to affect the structure of the action of the medium on the zeolite component.

In table. 1 contains the results of IR spectroscopic measurements deposited on active carbon of silicalite titanium. In the case described in the following examples according to the invention catalysts A, B and C band vibrations of Si-O-Ti is between 946 and 949 cm-1and in the case of pure silicalite titanium V, and in the case of a caution pravlenie proposed according to the invention supported catalysts silicate titanium - active carbon can be done in various ways. For example, activated carbon can be applied a mixture of TiO2- SiO2by co-precipitation and then to carry out the hydrothermal treatment in the presence of tetrapropylammonium within 24 to 240 h at 150 - 200oC.

Another option of cooking is the coprecipitation SiO2and activated carbon and subsequent impregnation of a mixture of C - SiO2using compounds of titanium and further hydrothermal treatment as described above.

As a source of SiO2serve, for example, liquid glass and Si(OC2H5)4. Suitable titanium compounds are known Ti OCl2and Ti(OC2H5)4.

Getting supported catalysts silicalite titanium oxide of the metal can be achieved by coprecipitation of a mixture of TiO2- SiO2in the presence of tetrapropylammonium within 45 240 h at 150 - 200oC.

The next option is the deposition of SiO2on the media with subsequent impregnation of the mixture of carrier-SiO2using compounds of titanium and further hydrothermal treatment in the presence of the template.

A third possibility ablauts">

As the source of TiO2also use TiOCl2and Ti(OC2H5)4and as a source of SiO2and liquid glass and Si(OC2H5)4.

A further object of the invention is the application of the proposed invention catalysts for oxidation reactions under mild conditions, for example, at 20 - 120oC and pressures equal to or above atmospheric pressure, and using H2O2< / BR>
Proposed according to the invention catalysts are also very effective for the following reactions: hydroxylation of aromatic hydrocarbons, the oxidation of saturated hydrocarbons, the oxidation of olefins, oxidation of allyl alcohol, the oxidation of alcohols.

Particularly preferably, these catalysts are used to obtain Akimov by catalytic conversion of the corresponding carbonyl compounds.

Unexpectedly found that these catalysts on a carrier in the case of conversion of ketones with NH3and H2O2also without prior activation with H2O2and H2SO4clearly possess higher activity than catalysts based on pure silicalite titanium (see table.1).

SST>2carry out when using deposited on the activated carbon is proposed according to the invention as catalyst in molar ratios of H2O2: carbonyl compound = 0,8 - 1,2; molar ratios of NH3: carbonyl compound = 1,2 - 2,5, at 20 - 120oC, a pressure equal to or higher than the atmospheric pressure, in water and in organic solvent, with vigorous stirring.

If used for this purpose applied to the oxide of the metal is proposed according to the invention the catalyst that set the molar ratio of H2O2: carbonyl compound = 0,8 - 2,0.

In the process the catalyst, the solvent and ammonia loads to the reactor together, and H2O2and the carbonyl compound is administered separately and simultaneously through the dosing device, and the speed dosing for H2O2and carbonyl compounds should not exceed 0.5 mmol or, respectively, 0.4 mmol per 1 kg of catalyst in 1 hour

High outputs oxides receive, when the concentration of the catalyst deposited on activated carbon of silicalite titanium is a value ranging from 0.02 to 30 g per 1 mol of carbonyl compounds. Especially blahop nalnogo connection. For the deposition of the metal oxide silicate titanium concentration of the catalyst are in the range of 0.05 - 30 g, preferably 1 to 8 g per 1 mol of carbonyl compounds.

To achieve high selectively and activities favorable temperature reactions 60 - 90oC and a slight excess pressure of 200 to 700 Torr.

This high activity against maximiliane or oxidation, as mentioned above, due to related interaction silicalite titanium with the media distortion of the lattice of the zeolite.

When applying the proposed catalysts for the above reactions it is essential that the content silicalite titanium in the catalyst on the carrier was 1 to 90 wt.%, better 10 - 90 wt.% and preferably 40 to 60 wt.%, when using activated carbon as a carrier and 30 - 50 wt. % when using a metal oxide as a carrier, and that the atomic ratio of Si/Ti was a value ranging from 10 to 100.

The size of the catalyst particles less than 63 microns. Particularly favorable for the implementation of this method in an industrial environment is the interval size of the grains of the catalyst 8 to 30 microns.

Get causatory characterized using methods b) and C):

a) infrared spectroscopy to determine the position of the strip vibrations of Si-O-Ti (tablet obtained by pressing EHF).

b) x-Ray determination of the volume of the unit cell (AAA) deposited on active carbon silicalite titanium.

Calculation of the volume of the unit cell of the zeolite components carried out on the basis of radiographic precision measurements of five interferences with strong intensity(501), (051), (151), (303) and (133) in the angular range from 2 v = 23,0oto 2 v = 25,8ousing Ni-filtered Cu K radiation when using a goniometer with the reference horizontal (Horizontalzhlrohrgoniometer) HZG 4/8 company Freiberger Przisionsmechanik GmbH (shooting conditions, step width 2 v = 1/100o; time/measurement point t = 60 sec, aperture differences bdiv= 1,09 mm; aperture counter bz= 0.13 mm). To establish certain water content of the sample before measuring stand at least 12 hours over a saturated solution of MgCl2.

Determine the position of the lines assigned to the internal standard (corundum), with Peak - Such-program. Used to calculate the volume of the elementary cell of the computational program proceeds from the monoclinic symmetry of the lattice, which includes the classification of IUPAC for calcined ZSM-5-zeolite).

C) determination of the catalytic activity in the reaction between cyclohexanone with ammonia and H2O2obtaining cyclohexasiloxane.

In table.1 shows the volumes of the unit cells for clean silicalite titanium as a comparative catalyst Cpand for proposed according to the invention the catalyst on the carrier silicalite titanium - activated carbon a, B and C; in addition to not containing media silicalite titanium, which is produced by burning coal from proposed according to the invention catalyst And at 500 - 550oC, and deposited on the metal oxide catalysts G - I. In the syntheses shown in table.1 proposed according to the invention catalysts, install Ti/Ti + Si) - value of 0.06.

The data in the table.1, show that the unit cell is supported on a carrier silicalite titanium is exposed to a strong reduction. After careful burning of active coal volume element of the cell again becomes the same size as in the case of pure silicalite titanium.

Affecting the structure of the action of the medium on the zeolite component is also shown by the results of IR spectroscopic measurements.

In sloco 949 cm-1and in the case of pure titanium silicate (catalyst), and in the case gently scorched catalyst on the carrier a-1, this band is located at 967 respectively 966 cm-1.

In table.2 shows the catalytic activity and selectivity of the proposed catalysts. The results clearly explain their advantages, particularly in relation to the high yield of the oxime with high selectivity.

Advantages of the invention also consist in the fact that

catalysts do not require any prior activation with H2O2and H2SO4;

the flow of catalyst below;

produce less by-products and

need a smaller number of expensive titanium silicates.

Moreover, when applying it turns out that the printed media silicates, titanium is better to manipulate, which in turn is caused by the particle size of 63 μm with a maximum particle size distribution in the region of 8 to 30 μm.

Example 1 (comparative). To 54,4 g tetraethylorthosilicate in nitrogen atmosphere and with stirring, add 2.4 g of tetraisopalmitate. This mixture dropwise then mixed with 120 g of the solution of tetrapropoxide am the P>C, incubated 1 h At this temperature and then heated at 98oC to remove isopropanol. After cooling, the liquid volume was adjusted to 200 ml with distilled water. The resulting product is treated in an autoclave at 175oC and autogenous (self) pressure for 10 days. Then the reaction product is cooled to room temperature, filtered, washed to pH 7, dried for 15 h at 120oC and then for 10 h, annealed at 420oC. Then the catalyst is treated at 70oC for 2 h using a mixture of 10 cm3H2O2(30 wt.%) 100 ml 100 ml H2SO4(5 wt.%) under stirring.

The liquid is then separated by decantation and processing using H2O2- H2SO4repeat twice more. The crystalline product is washed until pH 7 is dried for 15 h at 120oC and then calcined 2 hours at 550oC.

The product is indicated in the table.2 as the catalyst Cu (particle size 5 μm).

Example 2. To 78,66 g tetraethylorthosilicate in the atmosphere of inert gas and with stirring of 2.21 g of tetraethylorthosilicate. Then to this mixture in the atmosphere inert under stirring at 78oC and diluted with 157,32 g of water. In this solution make 15 g of acid washed activated carbon from spruce wood (DAR CO., particle size < 32 μm). Homogeneous suspension at room temperature, transferred to a sealed Teflon autoclave, which was heated for 90 min to 175oC. the Reaction mixture was incubated for 120 h at this temperature and under autogenous pressure and stirring. After cooling to room temperature, open the autoclave and vegascasinoonline the product is separated on the Frit from the mother liquor, washed repeatedly with distilled water and then dried at 120oC for 6 h in air. Then the catalyst was heated to 550oC with a heating rate of 10oC/min in an atmosphere of inert gas (10 l/h) and incubated for 4 h at this temperature and then cooled in a stream of nitrogen to room temperature.

The product obtained indicate in example 2, only instead of 15 g of active charcoal in this example, add 20.7 g of active charcoal. Resulting product is designated as catalyst B.

Example 4. 86,5 ml of liquid glass (347 g of SiO2/l) dissolved in 500 ml of water. To this solution was added 30 g of active charcoal (DAR CO., a particle size of 32 μm). Received baulenas H2SO5(3.8 wt. %) until the pH - value of 5.8. Suspension after deposition additionally stirred for 30 min at room temperature. Deposited on active coal SiO2is filtered off, washed and dried for 24 h at 80oC in air.

Then 8,48 g tetraethylorthosilicate in inert conditions, dissolved in 400 ml of ethanol. To this clear solution make a cooked product active coal SiO2. Resulting suspension in a vacuum rotary evaporator in vacuum 16 mbar bring up to obtain dry media. The impregnated carrier is suspended in 690 g of a 20% aqueous solution of tetrapropylammonium and 640 g of water and transferred into an autoclave, heated to 90 min to 175oC and incubated for 120 h at this temperature. After cooling to room temperature, open the autoclave and the product is separated on a filter from the mother liquor and washed repeatedly with water. Then the product is dried in air at 120oC over a period of time of 6 h and then with heating rate of 10oC/min heat up to 550oC in a stream of nitrogen, incubated 4 h at this temperature and then cooled in a nitrogen atmosphere to room temperature. The catalyst indicated in the table the atmosphere add to 78,66 g tetraethylorthosilicate. Then to this mixture in an inert atmosphere add 172,5 g of 20 wt.%-aqueous solution of tetrapropylammonium ammonium. This mixture is allowed to stand for 1 h under stirring at 78oC and diluted with 157,32 g of water. In this solution make 15 g of SiO2(surface: 385 m2/g, particle size < 32 μm). Homogeneous suspension at room temperature, transferred to a sealed Teflon autoclave and heated at 90 min to 175oC. At this temperature, the reaction mixture was kept at autogenous pressure. After cooling to room temperature, open the autoclave and the reaction product is separated from the mother liquor by filtration, washed repeatedly with distilled water and then dried at 120oC in air. Then the dried product is heated to 550oC with a heating rate of 10o/min in a stream of air (10 l/h) and prikalivaut h at this temperature. Then the catalyst was cooled to room temperature.

The resulting product is designated as catalyst,

Example 6. Proceed analogously to example 5, but instead of SiO2as the carrier used 15 g of Al2O3SiO2(20 wt.% SiO2the surface 226 m2/g, a particle size of 32 μm). The catalyst tablesto media use 17 g of ZrO2(15,6 m2/g, a particle size of 32 μm). The catalyst in the table. 1 and 2 indicates as a catalyst E.

Example 8. in 21.6 ml of liquid glass with the content of SiO2347 g/l dissolved in 125 ml of water. To this solution was added 7.5 g-Al2O3(186 m2/g, particle size < 32 μm). This suspension is stirred for 20 min at room temperature and then for 20 min, precipitated with dilute H2SO4(3.8 wt.%), up to a pH - value of 5.9. After that, the suspension is further stirred for 30 min at room temperature, SiO2deposited on Al2O3, is filtered off, washed and dried for 6 h at 120oC in air. Then of 2.21 g of tetraethylorthosilicate in an inert atmosphere quickly dissolved in 100 ml of ethanol. In this solution make the product Al2O3- SiO2. Resulting suspension is treated in a vacuum rotary evaporator at a vacuum of about 16 mbar, viparita up dry mixture of solids. The mixture is suspended in 172,5 g of 20 wt.%-aqueous solution of tetrapropylammonium ammonium and 160 g of water and transfer to a sealed Teflon autoclave. This suspension is heated to 90 min to 178oC and kept at this temperature for 120 hours After cooling, and washed repeatedly with water. The product is then dried in air for 6 h at 120oC, and then heated with a heating rate of 10oC/min in air 550oC, kept at this temperature for 3 h and then cooled to room temperature. The resulting product is designated as catalyst J.

Example 9. Proceed as in example 8, but instead of Al2O3use 16 grams of TiO2(21, m2/g, a particle size of 32 μm). The resulting product is a catalyst HW

Example 10. Proceed as in example 8, but instead of Al2O3for the preparation of the catalyst, a mixture of 5 g of ZrO2, 4 g-Al2O3and 6 g of SiO2. Received the product in the table. 2 indicate how the catalyst And.

Example 11. Determination of catalytic activity proposed according to the invention catalysts and the comparative catalyst is carried out at their use in the reaction between cyclohexanone with ammonia and H2O2obtaining cyclohexasiloxane.

For this purpose, the reaction vessel every time download 1.0 g of catalyst, 48 ml of NH3H2O (to 13.8 wt.%) and 42 ml of tert.-butanol. This suspension under vigorous stirring heated to 80o2O2(30%) and 17 g of cyclohexanone. Then the reaction mixture was incubated for another 30 min at the reaction temperature and then cooled to room temperature. During the reaction is first installed high pressure 630 - 760 Torr, which is at the end of the reaction is reduced to a value of about 300 Torr.

For processing of the reaction mixture, the catalyst is removed by centrifugation, and the liquid product is mixed with 20 ml of cyclohexane, which is primarily used for washing equipment, and 20 g of ammonium sulfate. After extraction for 5 min, the phases are separated and the aqueous phase is extracted another five times each time with 10 ml of cyclohexane. The organic extracts are combined and analyzed by gas chromatography. The test results are given in table. 2.

Example 12. In purged with nitrogen, the autoclave (capacity 200ml) load of 7.4 g of n-hexane, 17.8 g of acetone, 17,5 g H2)2(35%) with 0.25 g of catalyst Cpor, respectively, 0.3 g of catalyst 3 (corresponds to the content of zeolite 0.15 g). In the reaction mixture interact for 60 min at 95oC and under stirring (600 rpm for 1 min) and then after cooling to room temperature it is measuring. While n-hexane excellentpis 54%, in the case of proposed according to the invention the catalyst 3, it is 63%.

Example 13. 48 g of heptane-1-ol, 80 g of acetone and 6.5 g of catalyst Cpor, respectively, 12 g of the proposed catalyst D (corresponds to the content of zeolite 5.8 g) is placed in a equipped with a reflux condenser, the reaction vessel is heated to 65oC, then for 30 min mixed with 10 g of H2O2(35%) and then incubated with stirring. After cooling to room temperature the reaction mixture is analyzed. Catalyst Cpin heptanal turn 14.5% of heptanol, and the application of the proposed catalyst D in heptanal become 16,8% heptanol.

Example 14. In the reaction vessel is placed 12 g of allyl alcohol, 30 g of tert.-butyl alcohol, 100 g of water, 22 g of H2O2(35%) together with 3.5 g of catalyst Cpor respectively of 6.9 g of the proposed catalyst D (corresponding to 3.4 g of zeolite) and stirred for 8 h at 30oC. Then the reaction mixture is analyzed. In the case of catalyst Cpthe output of the glycerin is to 78.2% in the calculation used allyl alcohol, and the use of the proposed catalyst D output glycerin is 83.7 percent.

oC. Then the reaction mixture is cooled and analyzed. The analysis shows the degree of conversion of phenol to 28.9% for catalyst Cpand 30.9% for the proposed catalyst J. the composition of the reaction product in both cases is a 48% hydroquinone and 52% of catechol.

Example 16. 10 g of Oct-1-ene and 40 g of methanol each time together with 4.5 g of catalyst Cpaccordingly 6 g of catalyst E (corresponds to the content of zeolite 2.9 g) or, respectively, 6.4 g of a catalyst (corresponds to the proportion of zeolite 3.2 g) is introduced into the reaction vessel and heated to 48oC. Then, each time added dropwise 5 g H2O2(35%) under stirring. After a reaction time of 90 min, the reaction mixture was cooled and analyzed. You get the results shown in the table.1.

Examples 12 to 16 clearly show that the activity in the oxidation process in the calculation of the proportion of zeolite in the case supported on a carrier of silicalite titanium higher than the activity of the zeolite phase without media.

1. Catalyst for oxidation of organic compounds based on silicalite titanium with the MFI structure, characterized in that it further comprises a media - activated carbon or a metal oxide and is cristallin respect to silicon : titanium 10 - 100.

2. The catalyst p. 1, characterized in that it contains 10 to 90 wt.% silicalite titanium.

3. The catalyst p. 2, characterized in that it is a crystallizing media - active coal silicalite titanium content silicalite titanium 40 - 60 wt.%.

4. The catalyst p. 2, characterized in that it is a crystallizing media - metal oxide silicalite titanium content silicalite titanium 30 - 50 wt.%.

5. The catalyst PP.1, 2, or 4, characterized in that as the carrier is a metal oxide it contains aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, aluminum oxide-silicon dioxide or a mixture of oxides.

6. The catalyst PP.1 to 5, characterized in that the volume of the unit cell of the phase silicalite titanium supported on a carrier, is less than the volume of the unit cell corresponding silicalite titanium without media.

7. A method of producing a catalyst for the oxidation of organic compounds, including processing of precursor silicalite titanium autoclave in the presence of organic nitrogen compounds under autogenic pressure at elevated temperature, characterized in that predshestvennki or by depositing silicon dioxide on activated carbon followed by impregnation compound of titanium, when this processing predecessor silicalite titanium is carried out at 150 - 200oWith within 24 to 240 hours

8. The method according to p. 7, characterized in that the application of the predecessor silicalite titanium is carried out by deposition of a mixture of silicon and titanium dioxide on activated carbon.

9. The method according to p. 7, characterized in that the application of the predecessor silicalite titanium is carried out by deposition of dioxide silicon on activated carbon followed by impregnation compound of titanium.

10. A method of producing a catalyst for the oxidation of organic compounds, including processing of precursor silicalite titanium autoclave in the presence of organic nitrogen compounds under autogenic pressure at elevated temperature, characterized in that the precursor silicalite titanium obtained by coating a metal oxide on titanium containing crumpsall, or a mixture of titanium dioxide - silicon dioxide to metal oxide or silicon oxide on the metal oxide with subsequent impregnation compound of titanium, processing of precursor silicalite titanium is carried out at 150 - 200oWith 48 - 240 h, followed by washing, filtration and heat treatment.

11. The method according to p. Rasim kremnezem metal oxide.

12. The method according to p. 10, characterized in that the application of the predecessor silicalite titanium is carried out by deposition of a mixture of titanium dioxide and silicon dioxide on the metal oxide.

13. The method according to p. 10, characterized in that the application of the predecessor silicalite titanium is carried out by deposition of silicon dioxide on the metal oxide with subsequent impregnation compound of titanium.

14. The method of obtaining Akimov through catalytic interaction of the corresponding carbonyl compounds with ammonia and hydrogen peroxide in the presence of a catalyst, characterized in that the use of catalyst comprising a crystallizing in situ on the carrier is activated carbon or a metal oxide - deposited silicalite titanium with MFI-structure content silicalite titanium 1 to 90 wt.% and the atomic ratio of silicon : titanium 10 - 100, the interaction is carried out at a temperature of 20 - 120oWith pressure equal to or higher than the atmospheric pressure, in water or an organic solvent under vigorous stirring.

15. The method according to p. 14, characterized in that the use of the catalyst according to PP.1 to 3 and 6, when a molar ratio of H2O2: carbonyl compound is 0.8 to 1.2, when the molar aout the catalyst PP. 1,2 and 4 to 6 at a molar ratio of H2O2: carbonyl compound 0,8 - 2,0, a molar ratio of NH3: carbonyl compound 1,2 - 2,5.

17. Way catalytic hydroxylation of aromatic hydrocarbons in the presence of a catalyst, characterized in that the use of the catalyst according to PP.1 - 6.

18. The method of oxidation of hydrocarbons and alcohols using a catalyst based on silicalite titanium with the MFI structure, characterized in that the use of the catalyst according to PP.1 - 6.

19. The method according to p. 18, characterized in that the use of the catalyst according to PP. 1, 2, 4 - 6 for the oxidation of saturated hydrocarbons.

20. The method according to p. 18, characterized in that the use of the catalyst according to PP.1 - 6 for the oxidation of olefins.

21. The method according to p. 18, characterized in that the use of the catalyst according to PP. 1 - 6 for oxidation of allyl alcohol.

22. The method according to p. 18, characterized in that the use of the catalyst according to PP.1 - 6 for the oxidation of alcohols to aldehydes.

 

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