Method for production of phenol and its derivatives and method for the oxidation of benzene and its derivatives

 

The invention relates to a method of selective oxidation of aromatic compounds (e.g. benzene and its derivatives) in gidroksilirovanii aromatic compounds (for example, into the corresponding phenols). The methods include a mixture of aromatic compounds with nitrous oxide at a temperature of reaction between 225-500oWith and impact on a mixture of heterogeneous catalyst, which contains the high-silica zeolite type pentasil in acid form. The catalyst is subjected to pre-activation, comprising the following stages: heating the zeolite at 350-550oWith the current of inert gas or air within 4-6 h; calcining the zeolite at 550-1100oC for 1-3 h in the continuous current of inert gas or air and cooling the zeolite catalyst to the reaction temperature, resulting in the composition of heterogeneous catalyst. The preferred catalyst for this process is a composition comprising a high-silica zeolite type pentasil (for example, type zeolite HZSM-5), with a ratio Si/Al of 20 to 50, including gallium in relation to the silicon/gallium from 40 to 100. The impregnated zeolite is calcined in air flow at 550-800oC. the Molar ratio of N2O:the substrate is s, forfinally, divertingly, dialkylphenol, where alkyl With1-C3. The technical result - the performance improvement process with a high selectivity of the oxidation reaction using nitrous oxide and modified the high-silica zeolite. 2 C. and 17 C.p. f-crystals, 7 PL.

This application pritate a right of priority in accordance with section 35, United States Code, 119, on the basis of the application for patent of Russia 97112675 filed July 5, 1997

Field of invention This invention relates to the field of organic synthesis and, in particular, relates to methods of obtaining hydroxylated aromatic compounds (for example, phenol and its derivatives by selective oxidation of aromatic compounds (e.g. benzene and its derivatives) gas mixtures containing nitrous oxide (N2O) in the presence of heterogeneous catalysts. As heterogeneous catalysts used industrial zeolites or containing zeolite catalysts modified by special processing described here.

Background of invention In the technique known various methods for production of phenol and its derivatives, such as definaly, chlorophenols, fortunaly, Alki what Sloboda, N2O or other gaseous oxidants in the presence of oxide catalysts, such as catalysts, are described in U.S. patent 5110995. However, the majority of known oxide catalysts for direct oxidation of benzene to phenol in the presence of molecular oxygen does not provide high selectivity and yield of the target product. The most successful example of such a catalyst is a catalyst derived from phosphates of various metals. In particular, ZnPO4used as catalyst for the oxidation of benzene to phenol in the presence of alcohols. At temperatures of 550-600oWith the catalyst ZnPO4let phenol of about 25%. However, the selectivity of ZnPO4was low (60%) [Patents Japan 56-77234 and 56-87527, 1981]. In addition, phosphate catalysts are disadvantageous for benzene oxidation, as in their application consumed significant amounts of alcohol.

Known oxide catalytic systems based on vanadium, molybdenum or tungsten for the direct oxidation of benzene with nitrous oxide (N2O) at 500-600o[Iwamoto et aL, J. Phys. Chem., 1983, v. 87, 6, p. 903]. The maximum yield of phenol for such catalysts in the presence of excess water vapor is about 7-8% with a selectivity of 70-72%.

The basics of the market, required for the reaction, and the need to add a pair.

Zeolite catalysts are also used for the selective oxidation of benzene and its derivatives using as oxidant N2O (E. Suzuki, K. Nakashiro, Y. Ono, Chem. Lett., 1988, 6, born 953; M Gubelmann et al. European patent 341165, 1989; M. Gubelmann et al., U.S. patent 5001280, 1990). In particular, high-silicon zeolites ZSM-5 type pentasil were used as catalysts for the oxidation of benzene, chlorobenzene and fervently into the corresponding phenols. The oxidation of benzene with nitrous oxide on the zeolite HZSM-5 at 400oWith leads to the formation of phenol with access to 16% and a selectivity close to 98-99%.

The disadvantage of these catalysts is that they give a low degree of conversion, the low outputs of phenol and low selectivity at high temperature reactions. Zeolites of type pentasil (for example, ZSM-5, ZSM-11, ZSM-12, ZSM-23), mordenite, zeolite beta and EU-1, which is modified by small additions of iron during their synthesis are known systems for the implementation of this catalytic reaction. For example, in U.S. patents NN 5672777 and 5110995 presents experimental results on the oxidation of benzene with nitrous oxide at 275-450oC. the contact Time was 2-4 with, the volumetric rate is usually reached 20-30%, and the selectivity was 90-97%.

The disadvantages of these catalysts include the need to enter into the zeolite, iron ions and to control the degree of oxidation of the iron ions, low volume velocity of the fluid for benzene, significant contact time required to obtain an acceptable, but not impressive outputs of the final product, and low selectivity at elevated temperatures (~450oC).

Catalyst type HZSM-5, which dehydrosilybin at high temperatures, also known in the art (V. L. Zholobenko, Mend. Commun., 1993, p. 28). It was found that this treatment - degidroksilirovanie at high temperature increases the yield of phenol from ~12 to ~20-25 wt.% when the ratio of N2O:benzene, equal to 4:1.

However, this catalyst also gives a low yield of phenol. In the way described above, high-temperature degidroksilirovanie carried out in one stage, without control over the nature of the active sites of the zeolite. So in this way the formation of active centers in frame and out of frame, it's quite possible. A significant drawback of all these methods is that they require a large excess of N2O with respect to hydrocarbon (e.g. benzene) to provide a more complete one accepts ante Panova, I. and others (PCT WO 95/2791). This method was used in an excess of benzene with respect to N2O (up to 9:1), and the selectivity of conversion of N2O phenol has been improved.

However, in this case, the catalyst contained iron as the active component. Such catalysts have problems, as it is necessary to control the oxidation state of iron entered in this catalyst. In addition, the yield of phenol barely exceeds 20 wt.%, although hourly space velocity of fluid (hereinafter referred to here as the "LHSV") for benzene was increased compared with the previous systems until about 2-2,5 h-1.

In another known method, the phenol get the oxidative hydroxylation of benzene and its derivatives with nitrous oxide at 225-450oWith the presence of iron-containing zeolite catalyst. This zeolite catalyst is pre-heated at 350-950oWith in a steam atmosphere containing 0.1 to 100 mol. % H2On (Kharitonov A. S. and others, U.S. patent 5672777, 1977 - patent of Russia 2074164, C 07 C 37/60, June 1997-1, the application 94013071/04, C 07 C 37/60, 27.12.1995).

However, treatment of the zeolite catalyst in this way does not give a significant increase activity. Another disadvantage of this method is the low stability receive the software products. Another drawback of all the methods described above are low partial pressure of benzene in the vapor mixture benzene content was 5 mol.%, and the partial pressure of benzene was about 40 Torr.

Thus, the purpose of the present invention is to develop a method of obtaining a hydroxylated aromatic compounds (for example, phenol and its derivatives by selective oxidation of aromatic compounds (e.g. benzene and its derivatives). In particular, the purpose of the invention is to use the N2O as a mild oxidant in the presence of an appropriate catalyst, which improves the performance of the oxidation process results in increased yield of hydroxylated aromatic compounds and the selectivity to the target product. Another objective of the invention is to simultaneously minimize the consumption of N2O by reducing the relationship of the oxidant to carbon in the initial mixture and to increase the conversion efficiency of N2O in the desired oxidation products. In addition, the purpose of this invention is to avoid receiving side products.

Summary of the invention Objectives of this invention, the wasp is its derivatives) by oxidation of aromatic compounds (for example, benzene and its derivatives) nitrous oxide. The method of the present invention significantly increases the efficiency of the process due to increased activity and selectivity of the catalyst and increasing the yield of the target product (i.e., hydroxylated aromatic compounds).

In order to achieve these results, the aromatic compounds are oxidized using nitrous oxide when 225-500oIn the presence of zeolite catalyst. The zeolite catalyst according to this invention, modified acid-the main centres of the specific nature, containing a strong Lewis acid and base. These centers can be introduced in the zeolite catalyst by conducting special high-temperature processing. This preliminary thermal activation of H-form zeolite is carried out in two stages. In the first stage, the catalyst is heated at 350-450oC for 4-6 h in a flow of inert gas (nitrogen or helium) or air. In the second stage, the catalyst calcined at 450-1000oC for 1-3 h in a continuous flow of inert gas or air and then cooled zeolite catalyst to the reaction temperature (typically 300-450oC). In a preferred version of the invention hydroxyurea ablaut a benzene and its derivatives.

The applicants do not wish to be bound to any specific theory to explain the effect of the invention. However, the applicants propose the following explanation of how heat affects the catalyst. The purpose of the two-stage high-temperature processing is the generation of specific centers of the type containing a pair lisowska acid - base, preferably of Lewis sites of acid-base centres in the frame. This is achieved by separating the stage of removal of adsorbed water and/or ammonium ions (which are introduced by ion exchange at the stage of preparation of N - or-NH4-forms of zeolites) from the stage of removal of structural (bridge) Oh-groups in the framework of H-zeolites. With this purpose, heat treatment is performed in two stages. In the first stage, the zeolite is calcined at a temperature up to 350-450oFrom (common pre-processing). At this first stage intensively removes adsorbed water and put through the exchange of ammonium ions. In the second stage, the zeolite is calcined at temperatures in the range from 450 to 950oWith, depending on the composition of the zeolite. At the second stage removes structural (acid) and Oh-group zeolites. This second stage solves two problems is to implement a resinous products; and (2) the creation of new (aprotic), a relatively strong Lewis sites of acid-base pairs, preferably associated with the zeolite framework, which is able to activate molecules of N2O, to cause them to decay with the release of molecular nitrogen and the formation of atomic oxygen adsorbed on a strong Lewis sites of acid centers. Atomic oxygen acts as a mild oxidant in the reaction of selective oxidation of aromatic compounds to the corresponding hydroxylated aromatic compounds. Strong Lisovskii acid-base centers, which are the precursors of the active oxidative centers (atomic oxygen) can be determined using IR spectroscopy, using adsorbed molecule probes, such as CO, H2CH4and so on

Detailed description of the invention According to the present invention the starting materials for producing zeolite catalysts are industrial forms of zeolites, such as: (1) zeolites of type pentasil with a high silica content that is similar to ZSM-5, ZSM-11, etc. obtained, for example, as described in U.S. patent 3702886, which is included here by reference; (2) the zeolite H-mordenite; or (3) isomorphically substituted pentasil, such as eality ZSM-type (ZSMe-5, ZSM-11, ZSM-12, ZSM-23, and so on) with the relations Si/Al or Si/Me (where Me = Ga, Fe) more than 20. In more preferred versions of the invention, the ratio Si/Al or Si/Me is in the range from 40 to 100.

According to the present invention of the industrial zeolite is acidified by adding thereto an inorganic or organic acid. In a preferred embodiment of the invention, the acidified zeolite by impregnation his 10-100 ml of acid per gram of zeolite, where the acid has a normality of from 0.1 G. to 2n. The acid impregnation can be carried out in one stage or, more preferably, in several stages.

The acid form of the zeolite can also be prepared by ion exchange of industrial zeolite with an aqueous solution of ammonium salt (e.g., nitrate or chloride). For example, the Na-form of zeolite ZSM treated with 0.1 to 2n. the solution of the corresponding ammonium salts. The degree of ion exchange of the sodium ammonium ion or proton ranges from 30 to 100%, and more preferably from 50 to 95%.

Zeolites can be used as catalysts in pure form or mixed with a suitable binder. In a preferred embodiment of the invention in use as a binder of amorphous silica with a specific surface area of from 100 to 600 m2/g, or oxide and which is in the range of 5 to 50 wt.% and more preferably from 20 to 30 wt.%.

Nitrous oxide can be used in pure form or in mixture with an inert gas such as nitrogen or helium, or in a mixture with air.

Aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, cumene, xylenes, etc., halogenated aromatic compounds such as chlorobenzene, torbenson, differently etc., phenol, styrene or a mixture thereof, typically used as substrates for the selective oxidation of nitrous oxide. It is also possible additionally to selectively oxidize aromatic compound such as phenol, using the method described here. For the purposes of this description, these substances, which are the substrates will normally be called "aromatic compounds".

In this method, the substrate is mixed with nitrous oxide at a molar ratio of nitrous oxide to the substrate is from 1:7 to 5:1 and more preferably from 1:2 to 4:1. LHSV of the substrate is in the range from 0.2 to 5 h-1more preferably from 0.5 to 2 h-1. The reaction is preferably carried out at a temperature from 300 to 500oS and more preferably from 250 to 450oC. the contact Time of the reaction mixture with the catalyst is in the range from 0.5 to 8 and more preferably from 1 to 4 C.

Gases leaving the reactor can with the Asti techniques (gas chromatography, liquid chromatography, mass spectrometry or a combination of them).

The catalyst can be easily and reversibly be regenerated by calcination at 400 to 600oWith the current of air, oxygen and nitrous oxide or their mixtures with inert gas. Regeneration is carried out in 1-3 hours

In order to further illustrate the present invention and its advantages are the following specific examples, and it should be understood that they are illustrative only and in no way limit the invention.

In these examples below use the following parameters: C= percent conversion, S=selectivity in percent; Y=output per last product, Y=CS. The specifications shown in the examples are averages over two hours of continuous flow process.

Example 1 Synthesis of the original zeolite HZSM-5 was performed as described in U.S. patent 3702886, which is included in this description by reference.

Experimental conditions the oxidation of nitrous oxide: vapor phase - Continuous
The catalyst is HZSM-5 (SiO2/Al2O3=42)
Standard temperature pre-treatment - 350oWith
High-temperature annealing at,oWith- 450, 650, 750, 850, 920 or 1100
the and HZSM-5 (Si/Al= 21) in powder form (particle size 0.2-0.5 mm), dispersed in 400 mg of quartz sand with granules of the same size, was placed in a tubular reactor made of quartz or stainless steel (inner diameter 7 mm). Before the reaction, the catalyst was pre-treated in two stages. In the first stage, conducted the conditioning catalyst for 5 hours at 350oWith in a stream of nitrogen or air (60 l/min) in a tube furnace. In the second stage conducted soft high-temperature annealing comprising heating the catalyst for a further two hours at high temperature(450, 650, 750, 850, 920 or 1100o(C) in a continuous stream of nitrogen or air. After this treatment the catalyst was cooled to the reaction temperature (i.e., 350o(C) in a stream of nitrogen. The reaction was carried out continuously by introducing a mixture of benzene with a bulk velocity (LHSV) of 0.5-2 h-1nitrous oxide and helium (nitrogen). The contact time of the mixture was 1-4 C.

Data conversion, selectivity and yield of phenol depending on the final temperature of high-temperature pre-treatment are presented in table.1. In addition, in table.1 shows the percent of decontamination (i.e., the decrease in conversion over the next 60 min process). As can be seen from this table, the high-temperature bronchiale increases catalytic activity. At temperatures above 1000-1100oSince there is a destruction of the structure of zeolite HZSM-5, resulting in a drop of activity.

Example 2
The preparation of the catalyst and the tests were carried out as described in example 1, except that used a higher reaction temperature, 450oC. the data Obtained are shown in table.2.

These data show that if you use a higher temperature (for example, about 450oC) activity and especially the selectivity of the catalyst increases with increasing temperature high temperature annealing. So for catalyst developed in the present invention, the reaction of the direct oxidation of benzene to phenol proceeds with selectivity close to 100%, even at high temperatures of reaction.

Examples 3 and 4
The preparation of the catalyst and the tests were carried out as in examples 1 and 2, respectively, except that used other types of catalysts. In order to determine the dependence of the parameters of the catalyst from the ratio Si/Al in the framework of the zeolite, said zeolite HZSM-5 with a ratio Si/Al=50 (example 3) and zeolite HZSM-5 with a ratio Si/Al=21 (example 4). In these experiments, the partial pressure of benzene was 60-80 Torr. Rez is owned selectivity is maintained in a wide temperature range preliminary high temperature treatment.

Example 5
Zeolite HZSM-5 (Si/Al=21), obtained by treatment with acid or ion exchange NH4+as in example 1 was progulivali at 450oC for 5 h (cycle 1), then at 800oC for 2 h in a stream of air. After this treatment the catalyst was cooled to room temperature and kept in contact with water vapor for 24 h (cycle 2). Then the sample was again progulivali at 450, 650 or 800oC for 2 h and carried out the oxidation reaction of benzene and N2O at 350oSince, as described in example 1. The results of the catalytic experiments are presented in table.4.

These data show that the catalyst after pretreatment in conditions of high temperature annealing exhibits a higher activity than the original catalyst treated under standard conditions (~ 450oC). This remains true even if pre-treated catalyst is then hydratious and calcined a second time at 450-500oC. Thus, after Lisovskii acid-base centers that are associated with the lattice, formed, they remain at saturation water vapor, provided that the subsequent calcination is conducted at temperatures above 450oC.

Example 6 ugali in the reactor (particle size 1-2 mm). Benzene was served with a bulk velocity of 0.5 h-1and the ratio of N2O:C6H6was equal to 2: 1. The partial pressure of benzene was 120 Torr (the content of benzene in the vapor phase was equal to 16 mol.%). At the reaction temperature of 370oWith the release of phenol was equal to 25%, and the selectivity was 100%. At the reaction temperature of 420oThe output was 32% and a selectivity of 99%.

Example 7
2.3 g of the catalyst prepared according to example 3 and pre-treated at 900oWith, was loaded in the reactor (particle size 1-2 mm). Benzene was served with a bulk velocity (LHSV) of 0.3 h-1and the ratio of N2O:6H6was equal to 1:1. At the reaction temperature of 370oWith the release of phenol was 37%, and the selectivity was 100%. At 420oThe output was equal to 49%, and the selectivity was 99%. The efficiency of use of N2O for the selective oxidation of benzene to phenol was equal to 98%.

Example 8
2.3 g of zeolite HZSM-5 (particle size 1-2 mm) with the ratio of Si/Al=40 prepared according to example 3, was preliminarily heated at 850oFrom and loaded into the reactor. Benzene was served with a bulk velocity of 0.5 h-1and the ratio of N2O: C6H6was equal to 0.5:1. When the reaction temperature 400oWith the release of phenolates of 14.2%. At 420oWith the release of phenol in the calculation of the N2O was 33.6%, and the selectivity was equal to 98%. On the other hand, output per benzene was equal to 16.8%. The efficiency of use of N2O for the selective oxidation of benzene to phenol was 96%.

Example 9
2.3 g of zeolite HZSM-5 (particle size 1-2 mm) with the ratio of Si/Al=40 was obtained according to example 3, was preliminarily heated at 850oFrom and loaded into the reactor. Benzene was served with a bulk velocity of 0.3 h-1and the ratio of N2O:C6H6was equal to 0.5:1. At a temperature of 420oWith the release of phenol in the calculation of the N2O was 28,2%, and the selectivity was 98%. The efficiency of use of N2O for the selective oxidation of benzene to phenol was 95%.

Example 10
2.3 g of zeolite HZSM-5 (particle size 1-2 mm) with the ratio of Si/Al=40 was obtained according to example 3 was pre-treated at 850oFrom and loaded into the reactor. Benzene was served with a bulk velocity of 0.5 h-1and the ratio of N2O: C6H6was 1:1. As the oxidant used a mixture of N2O air (1: 3). At a temperature of 370oWith the release of phenol was equal to 26.8%, and the selectivity was 98%.

Example 11
Zeolite HZSM-5 (Si/Al=40) were extrudible with swazoo is Anna in example 1. The end temperature of the high temperature treatment was 900oC.

The catalyst used in the oxidation of benzene N2O. In this test space velocity (LHSV) of benzene was equal to 1.7 h-1, the molar ratio of benzene to N2O was 7:1 (large excess of benzene relative to N2O), and the temperature was 440-470oC. the Yield of phenol (N2O) was equal to 20.6% at 440oWith and 30.2% at 470oC. the Efficiency of use of N2O for the selective oxidation of benzene was 95-96%.

Example 12
Modified gallium zeolite HZSM-5 was prepared by impregnation of zeolite HZSM-5 with an aqueous solution of gallium nitrate and subsequent calcination at 500oC for 4 h to remove nitrate ions (contents GA2About3it was 3 wt.%). The zeolite is then pre-treated at 850oFrom and loaded into the reactor. Thus was treated with 2.3 g of zeolite (particle size 1-2 mm). Benzene was filed with the velocity (LHSV) of 0.5 h-1when the ratio of N2O:C6H6of 0.5:1. At the reaction temperature of 420oWith the release of phenol was equal to 20.8% in the calculation of the N2O or 10.4% for benzene. The selectivity was 100%. The efficiency of use of N2O for selectionguides according to example 3. This catalyst was diluted with quartz sand (750 mg) and the mixture was loaded into the reactor. As the substrate used benzene (example 13) and phenol (example 14). The ratio of nitrous oxide:the substrate was equal to 4:1, LHSV was 0.5 h-1and the reaction temperature was 430oC. In the case of benzene obtained a product containing 75% of phenol and 25% mixtures of o - and p-diphenols (in the ratio 1: 4). The total yield was 60%, and the selectivity was 97%. In the case of phenol was obtained a mixture of o-, m - and p-diphenols at a ratio of 1.0:0,5:4.0 with a total yield of 75%.

Examples 15-20
500 mg of the catalyst obtained according to examples 1 and 2 were placed in a flow-through installation. As the substrate used torbenson, o-, m - and p-differently, toluene, p-xylene, ethylbenzene and styrene (examples 15-20, respectively). The ratio of components in the gas mixture was as follows: No: air:N2O=1:3:5. LHSV substrate was 1-3 h-1. The ratio of N2O:the substrate was equal to 4: 1. Data on the oxidation of substrates are given in table.5-7. Several units conversion tables correspond to different reaction times (10, 40 and 70 min). It was observed that the conversion of alkyl benzenes (table.7) decreases with time. This observation can be explained by deactivation of the catalyst. In stevania m-isomer.

Example 21
Zeolite HZSM containing ions frame GA3+that were introduced during synthesis (Si/Ga=40) were subjected to high temperature processing by stepwise annealing at 450oC for 2 h Oxidation fervently conducted using this catalyst, while benzene LHSV was equal to 2.3 h-1the reaction temperature 400oWith, and part of the pelvic mixture was as follows: air: N2O: Not=3:5:2. The ratio of N2A:the substrate was 1:4. Under these conditions, the output terfenol was 20%, and the selectivity was 97%. Among the obtained tortenelem prevails para-isomer (70%).

In conclusion, we can say that the examples show that the catalysts proposed in the present invention, when applied for the oxidation of benzene and its derivatives into the corresponding phenols in the presence of nitrous oxide as an oxidizer, have the following advantages compared with the known catalysts, as described in the aforementioned patents:
(1) conversion of benzene to catalysts of this invention may be increased from 10-20% to 50-75% without reducing the selectivity (98-100%);
(2) selectivity conversion to phenol at high temperature reactions (400-470o(C) may be increased from 30-40% to 95-100%, and the output fizicheskih compounds may increase from 80-85% to 95-100%;
(4) if you are using a zeolite catalyst which has been subjected to a preliminary heat treatment, it is possible to apply a higher partial pressure of benzene and a lower ratio of N2O:benzene. This gives a reduction of nitrous oxide and increase the yield of phenol;
(5) the stability and lifetime of the catalyst can be significantly improved by modification of the zeolite catalysts by introducing a strong Lewis sites of acid-base centers. These centres have a specific nature and are formed by high-temperature calcination of the zeolite before testing them as catalysts;
(6) high yield and selectivity of the formation of phenol can be achieved without the introduction of special additives of iron in the catalyst and process steam;
(7) in some cases, the oxidation of benzene derivatives (for example, halogenated benzenes, phenols) process has a high selectivity and regioselectivity with respect to p-isomers phenols.

Although this invention has been described in various preferred options for its implementation, an experienced specialist will be able to determine what you can do various modifications, substitutions, deletions and other MEAs the Oia should not be limited to the preferred versions of the invention, as described here.


Claims

1. The method of obtaining gidrauxilirovannogo aromatic compounds by oxidation of aromatic compounds, in which the specified gidrauxilirovanne monocyclic aromatic compound has one hydroxyl group is greater than the specified monocyclic aromatic compound, the method includes: mixing a specified aromatic compounds with nitrous oxide at a reaction temperature in the range of 225-500oWith and impact on the specified nitrous oxide and a specified aromatic compound serving as a heterogeneous catalyst composition containing high-silica zeolite of the type pentasil in acid form, subjected to pre-activation, comprising the following stages: (a) heating the zeolite at 350-550oWith the current of inert gas or air within 4-6 h; (b) calcining the zeolite at 550-1100oC for 1-3 h in the continuous current of inert gas or air, and (C) cooling the zeolite catalyst to the reaction temperature, resulting in the composition of heterogeneous catalyst.

2. The method according to p. 1, characterized in that gidrauxilirovanne aromatic soy is the procedure under item 2, characterized in that the molecule aromatic compounds selected from the group consisting of benzene, phenol, fervently, chlorobenzene, 1,2-diferente, 1,3-diferente, 1,4-diferente, styrene and mono-, di - and trialkylated having alkyl groups containing from 1 to 3 carbon atoms.

4. The method according to p. 3, characterized in that the zeolite in the first stage, pre-activation is heated in a stream of nitrogen.

5. The method according to p. 1, characterized in that the high-silica zeolite of the type pentasil is an H-form ZSM-5 with a ratio Si/Al in the range from 20 to 50.

6. The method according to p. 1, characterized in that the ratio Si/Al is in the range from 30 to 50.

7. The method according to p. 1, characterized in that the reaction temperature is from 300 to 450oC.

8. The method according to p. 1, characterized in that the molar ratio2O:the substrate is in the range from 1:7 to 5:1.

9. The method according to p. 1, characterized in that the molar ratio2O:the substrate is in the range from 0.5:1 to 1:1.

10. The method according to p. 1, wherein the mixture of aromatic compounds and nitrous oxide add the diluent is an inert gas, and the diluent is chosen from the group consisting of N2Not and Ah.

11. The method according to p. 1, characterized in the C group, consisting of air and mixtures of air with inert gases.

12. The method according to p. 11, characterized in that the diluent is air.

13. The method according to p. 1, characterized in that the zeolite contains gallium and the ratio of silicon to Gaul ranges from 40 to 100.

14. The method according to p. 13, characterized in that after the synthesis of zeolite a zeolite impregnated with gallium salt and then calcined in the air.

15. The method according to p. 14, characterized in that the specified stage calcination is carried out at a temperature ranging from 550 to 800oC.

16. The method according to p. 1, characterized in that the composition of heterogeneous catalyst further comprises a binder, with the weight content of the binder is in the range from 5.0 to 50.0 wt.%.

17. The method according to p. 16, characterized in that the weight content of the binder is in the range from 10 to 30 wt.%.

18. The method according to p. 16, characterized in that the binder is chosen from the group consisting of silica, alumina and mixtures thereof.

19. The method of oxidation of aromatic compounds, including the interaction of the specified aromatic compounds with nitrous oxide at the reaction temperature 225-500o, Characterized in that it includes the implementation of aromatic contact soedineniya zeolite type pentasil in acid form, subjected to pre-activation, comprising the following stages: (a) heating the zeolite at 350-550oWith the current of inert gas or air within 4-6 h; (b) calcining the zeolite at 550-1100oC for 1-3 h in the continuous current of inert gas or air, and (C) cooling the zeolite catalyst to the reaction temperature, resulting in the composition of heterogeneous catalyst.

Priority points and features:
29.07.1997 on PP.4-7, 10, 13 and 15 for the whole set their attributes take precedence;
13.05.1998 on PP.9, 12 and 16-18 on the totality of their attributes take precedence;
29.07.1997 each of the paragraphs.1 and 19 takes precedence, except for the following characteristics:
"the reaction temperature in the range of 225-500oWith" - has priority from 29.07.1997 in part of the interval 225-450oAnd priority from 13.05.1998 in the rest of the specified temperature range;
"heating the zeolite at 350-550o" At the stage of (a) pre-activation process has a priority from 29.07.1997 in part of the temperature range 350-450oAnd priority from 13.05.1998 in the rest of the specified temperature range;
conducting the same stage (a) in a stream of inert gas or air has priority from 29.07.1997 applying air is th definition of gases, used in stage (a);
p. 2 has priority from 29.07.1997 in part of the following compounds: phenol, divinely, fortunaly and differenly, and priority from 13.05.1998 in part of chlorophenols;
p. 3 has priority from 29.07.1997 in part of the following compounds: benzene, torbenson, differental, p-, o-xylene, toluene, ethylbenzene, styrene, halogenases, and priority from 13.05.1998 as other compounds.

Sign p. 8 molar ratio of N2O:the substrate is in the range from 1:7 to 5:1 has priority from 29.07.1997 in terms of interval relations from 1:1 to 5:1 and priority from 13.05.1998 in the rest of the specified interval relations.

Sign p. 11 "type diluent, the diluent is chosen from the group consisting of air and mixtures of air with inert gases takes priority from 29.07.1997 in use as a diluent inert gas and priority of 13.05.1998 in terms of other possible diluents mentioned.

Sign p. 14, which consists in the impregnation of the zeolite after its synthesis gallium salt, has priority from 13.05.1998, and the sign of p. 14, consisting in the subsequent calcination in air, has a priority from 29.07.1997.

 

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The invention relates to medicine, namely dentistry

The invention relates to petrochemical synthesis of 2,6-di-tert-butyl-phenol alkylation of phenol isobutylester fraction in the presence of a catalyst of aluminum, dissolved in phenol, followed by separation of the desired product and impurities of alkyl phenols by distillation

The invention relates to organic synthesis, in particular the production of phenol and Cresols selective direct oxidation of benzene and/or toluene nitrogen oxide in the presence of a heterogeneous catalyst

The invention relates to the petrochemical industry, in particular the production of 2,6-di-tert-butyl-4-METHYLPHENOL (2,6-DTB-4-IC) method for the hydrogenolysis of N, N-di-methyl-(3,5-di-tert-butyl-4-oxybenzyl)-amine on the floatable nicolelovestitanic the catalyst for hydrogenating agent in the environment 2,6-di-tert-butyl-4-METHYLPHENOL at elevated temperature and pressure

The invention relates to the field of production of substituted phenols used as inhibitors of free radical processes

The invention relates to a method for production of phenol and its derivatives by oxidation of benzene and its derivatives nitrogen oxide in the presence of heterogeneous catalysts

The invention relates to the production of phenol and acetone Kukolnik method

The invention relates to methods of rational use of phenolic resin and obtaining useful products from it, in particular drugs for the protection of forest plantations from pests

The invention relates to a method for the synthesis of hydroxylated aromatic compounds by the oxidation of aromatic compounds with hydrogen peroxide in an organic solvent in the presence of synthetic zeolites

The invention relates to a method for production of phenol by direct gas-phase oxidation of benzene with nitrous oxide in the presence of industrial zeolites

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The invention relates to an improved method for production of phenol, acetone and-methylstyrene Kukolnik method and relates to the stage of acid decomposition of technical cumene hydroperoxide
The invention relates to pharmaceutical industry

The invention relates to organic synthesis, in particular the production of phenol and Cresols selective direct oxidation of benzene and/or toluene nitrogen oxide in the presence of a heterogeneous catalyst

The invention relates to the production of phenol and acetone by decomposition of technical cumene hydroperoxide (CHP)

The invention relates to a method for production of phenol and its derivatives by oxidation of benzene and its derivatives nitrogen oxide in the presence of heterogeneous catalysts

The invention relates to the field of organic synthesis, more specifically to a method for production of phenol and its derivatives by catalytic oxidation of benzene and its derivatives
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