Hydrocarbon conversion process, micro-mesoporous-structure catalyst for accomplishment thereof and catalyst preparation process

FIELD: petrochemical process catalysts.

SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T2O3(10-1000)SiO2, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula CnH2n+1(CH3)3NAn (where n=12-18, An is Cl, Br, HSO4-) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.

EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.

16 cl, 2 dwg, 2 tbl

 

The present invention relates to methods for the conversion of hydrocarbons using catalysts with micro-mesoporous structure. The invention can be used in the processes of the petrochemical, petroleum refining, and organic synthesis.

It is known that the microporous molecular sieves, such as zeolites and zeolite like materials, are catalysts in various processes of conversion of hydrocarbons. They have a strong acidity, high thermal and thermoprotei stability, as well as a developed system of pores of a certain size.

Zeolites of type LTL, MAZ, MEI, EMT, OFF, BEA, MOR, MEL, MTW, MTT, MFI, FER, TON widely used in reactions for the conversion of hydrocarbons, such as cracking of hydrocarbons, isomerization, transalkylation and disproportionation of alkylaromatic compounds, alkylation of aromatic hydrocarbons, the conversion of naphtha, paraffins and/or olefins to aromatics, conversion of oxygen-containing compounds in aromatic hydrocarbons (US 6160191).

Known use in alkylation reactions and transaminirovania aromatic compounds of the type zeolites BEA (US 4891458, US 6034291), ultrastable (with respect zeolite Y (patent US 4169111), ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 (US 4577048), mordenite (US 5243116), and MCM-22 in the isomerization of paraffins (US 5107054), H-ZSM-5 in the aromatization process Ugledar the Dov (US 5574199).

In the US 6194616 proposed the use of ZSM-4, L, ZSM-12, ZSM-22, ZSM-23, ZSM-48, Y, X, - ZSM-5, Beta, ZSM-11, offretite, chabasite as one, clinoptilolite, erionite, mordenite, phillipsite in the acylation of aromatic compounds.

All of the above traditional zeolites, both natural and synthetic, have a system of micropores with diameters less than 2 nm, which leads to difficulty of mass transfer of reactant molecules to the active centers of the zeolite, located within its channel, as well as the reaction products from the reaction zone, which reduces the efficiency of the zeolite, when used in the conversion of hydrocarbons. In addition, zeolites do not catalyze reactions involving large organic molecules (K.Tanabe, W.F.Holderich. // Applied Catalysis A: General, 181 (1999), 399-434).

With the advent of mesoporous molecular sieves, was first produced in 1992, tied large prospects in heterogeneous catalysis, as it was assumed that they will be widely used as catalysts in the transformation of large molecules (US 5098684, J.S.Beck, J.C.Vartuli, W.H.Roth et al. // J. Am. Chem. Soc. 114 (1992) 10834). In particular, it was planned use of mesoporous catalysts in refining oil for deep catalytic cracking, and in fine organic synthesis and pharmaceutical industry (D.Trong On, D.Desplantier-Giscard, C.Danumah, S.Kaliaguine. // Applied Catalysis A: General 222 (2001) 299-357).

Known usage the use mesoporous catalysts, modified by heteroatoms selected from the group of Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Pt or W, in the conversion of hydrocarbons, such as alkylation, acylation, oligomerization, selective oxidation, hydrobromide, isomerization, demeterova, catalytic dewaxing, hydroxylation, hydrogenation, dehydrogenation and cracking (US 6930219).

However, the application as catalysts mesoporous materials with large pore size (from 2 to 50 nm), leads to the formation of large amounts of side reaction products, which greatly reduces the selectivity of the formation of the desired products. In addition, as shown by subsequent studies, mesoporous molecular sieves have low resistance to water vapor and relatively low acidity. This was the reason that mesoporous catalysts have not received the real distribution.

Known use in the reactions of cracking, alkylation and isomerization micro-mesoporous catalyst, in which the microporous zeolite (Beta, Y or ZSM-5) is added to the inorganic oxide having mesopores with a diameter of from 3 to 25 nm (US 6762143).

Called the catalyst is characterized, first, by the presence of two phases: zeolite and inorganic oxide, each of which has disadvantages of micro - and mesopores is the simple catalysts, secondly, a wide size range of mesopores (from 3 to 25 nm), which leads to a low selectivity for the target products.

In the US 6558647 proposed micro-mesoporous catalyst based on zeolite Beta for hydrocracking of alkanes.

The catalyst has a limited scope due to the presence of only the structure of zeolite Beta.

The present invention is a technical problem to develop a method of converting hydrocarbons, which through the use of the catalyst micro-mesoporous structure would receive a wider variety of hydrocarbons with a good selectivity of their education.

The technical result is achieved by the fact that the proposed method of converting hydrocarbons, including the introduction of hydrocarbons in the conversion of hydrocarbons into contact with a catalyst with micro-mesoporous structure containing microporous crystalline silicates with zeolite structure having the composition of anionic skeleton T2About3(10-1000)SiO2where T - the elements selected from the group consisting of p-elements of group III or d-element IV-VIII group, or mixtures thereof, the micro-mesoporous structure is characterized by the share of micropores from 0.03 to 0.40 and the proportion of mesopores from 0,60 to 0.97.

The catalyst, which combines the advantages of zeolites and mesoporous molecules of the situations sieves, you can achieve greater catalytic activity and stability compared to microporous and mesoporous catalysts by increasing access of the reactants and products of reaction to the active centers of the catalyst.

Named catalyst has versatility and can be successfully used for various processes of obtaining hydrocarbons, selected from a number of processes involving the cracking of hydrocarbons, alkylation of aromatic compounds, transalkylating aromatic hydrocarbons, paraffin aromatization of hydrocarbons, the acylation of aromatic compounds, isomerization of paraffin hydrocarbons and the oligomerization of olefinic hydrocarbons.

These processes are characterized by a high selectivity of the formation of the desired products.

It is expedient conversion of hydrocarbons to carry out at temperatures from 220 to 550°s With gauge pressure of from 0.1 to 1 MPa, the feed rate of the raw material is from 0.5 to 5 g/g·h

The conversion at lower temperatures and pressures and at higher flow rates of the reactants leads to a noticeable decrease in the conversion of the feedstock. Carrying out conversion at higher temperatures and pressures and at lower flow rates of the reactants leads to a noticeable increase in the education side ol the products of the reaction, consequently, to a decrease in selectivity for the target reaction products.

It is advisable as microporous crystalline silicates to use silicates with the structure of zeolites FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW.

Suitable catalysts to further modify the metals selected from d-elements II and VIII groups, for example zinc, or platinum. The content of metals selected from d-elements II and VIII groups is from 0.1 to 2 wt.%.

This provides catalysts bifunctionality for use in such reactions as isomerization and/or aromatization of alkanes.

It is advisable to use in the process of conversion catalyst with micro-mesoporous crystalline structure of the original microporous silicate with acid centers with activation energy of desorption of ammonia 140-190 kJ/mol, the proportion of which is not less than 0.5.

The basis of the invention is also based on the technical problem of the creation of the catalyst micro-mesoporous structure and method of its preparation, which would have a high catalytic activity and would provide a high selectivity of the formation of the desired products in various processes for the conversion of hydrocarbons by maintaining the crystal structure of the original microporous crystalline silicate, and also due to the presence of regularly the system of mesopores.

The technical result is achieved by the features of the catalyst for conversion of hydrocarbons with micro-mesoporous structure, which according to the invention includes a microporous crystalline silicate with zeolite structure having the composition of anionic skeleton T2About3(10-1000)SiO2where T - the elements selected from the group consisting of p-elements of group III or d-element IV-VIII group, or mixtures thereof, the micro-mesoporous structure is characterized by the share of micropores from 0.03 to 0.40 and the proportion of mesopores from 0,60 to 0.97.

As T-elements, forming, along with the silicon atoms, the lattice silicate, use Al or Ga, or In, or Fe, or Zn, or Ti, or Zr, or V, or Cr, or a mixture.

The technical result is also achieved by the fact that the proposed method of producing the catalyst micro-mesoporous structure, including the suspension of microporous crystalline silicates with zeolite structure having the composition of anionic skeleton T2About3(10-1000)SiO2where T - the elements selected from the group consisting of p-elements of group III or d-element IV-VIII group, or mixtures thereof in an alkaline solution with a concentration of hydroxide ions is 0.2 to 1.5 mol/l to achieve a residual content of the zeolite phase in suspension 3-40 wt.%, introduction to the suspension of the silicate solution of the cationic surface-act the main substances in the form of a Quaternary salt of alkylamine composition With nH2n+1(CH3)3NAn, where n=12-18, An Is Cl, Br, HSO4-with the subsequent addition of acid to form a gel with a pH of 7.5-9.0 and hydrothermal treatment of the gel with 100-150°at atmospheric pressure or in an autoclave for 10-72 h with the release of the finished product, which is characterized by the share of micropores from 0.03 to 0.40 and the proportion of mesopores from 0,60 to 0.97.

The obtained micro-mesoporous catalyst has the structure of a microporous crystalline silicate with a zeolite with structure type FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW.

If necessary, the catalyst can optionally be modified by an ion exchange method or impregnation with salts of metals selected from d-elements II and VIII groups, mainly salts of zinc or platinum. The amount of damage modifier (metal selected from d-elements II and VIII groups) is from 0.1 to 2 wt.%.

Hereinafter the invention will be disclosed in detail in the description and examples of its implementation with reference to the accompanying drawings, in which, according to the invention

figure 1 depicts the powder diffraction pattern of the source and the obtained catalysts;

figure 2 depicts the low-temperature isotherms of adsorption-desorption of nitrogen source and derived catalysts.

The catalyst micro-mesoporous structure according to the invention is obtained by suspension m is croporate crystalline silicates with a zeolite structure, having the anionic composition of the frame T2About3(10-1000)SiO2in alkaline solution until the residual content of the zeolite phase in suspension 3-40 wt.%, introduction to the suspension of the silicate solution of cationic surfactant and then adding acid to gel formation and hydrothermal treatment of the gel with the release of the finished product.

The obtained micro-mesoporous catalyst retains the crystal structure of the original microporous crystalline silicate, as shown in figure 1. where curve 1 represents the diffraction pattern of microporous aluminosilicate structure MOR, curve 2 is the diffraction pattern of the catalyst micro-mesoporous structure, based on the aluminosilicate structure MOR, and curve 3 is the diffraction pattern of the silicate with known mesoporous structure, which is not crystalline.

The suspension microporous crystalline silicate is carried out in alkaline solution with a concentration of hydroxide ions is 0.2 to 1.5 mol/l, and alkaline suspension of zeolite is mixed with a solution of cationic surfactants and add acid to form a gel with a pH of 7.5 to 9.0. Hydrothermal treatment of the gel is carried out at a temperature of 100-150°at atmospheric pressure or in an autoclave for 10-72 hours

As cationic surface is chestno-active substances used Quaternary salt of alkylamine composition With nH2n+1(CH3)3NAn, where n=12-18, An Is Cl, Br, HSO4-providing electrostatic interaction between negatively charged (due to the adsorption of Oh-ions) finely dispersed fragments of the original crystals of silicate and silicate ions and the positively charged micelles surfactants. The result of this interaction is formed mesoporous phase.

Pore volume, the proportion of micropores and the proportion of mesopores calculated by isothermal low-temperature nitrogen adsorption, as shown in figure 2, where the curve 4 represents the low-temperature isotherm of adsorption-desorption of nitrogen for microporous silicate structure of zeolite MFI, curve 5 - low-temperature isotherm of adsorption-desorption of nitrogen for materials with micro-mesoporous structure, obtained on the basis of microporous silicate structure of zeolite MFI, curve 6 - low-temperature isotherm of adsorption-desorption of nitrogen for known silicate with mesoporous structure. As follows from figure 2, the isotherm of adsorption of micro-mesoporous catalyst (curve 5) is similar to the isotherm of mesoporous catalyst (curve 6), which indicates the formation of well-developed regular patterns. The location of the isotherms micro-mesoporous catalyst (curve 5) and microporous silicate (curve 6) indicates an increase about the EMA then 2.5 times.

A feature of the catalyst micro-mesoporous structure is the presence of two types of long - micropores (whose share in the total volume of the pores of the material is 0.03-0,40) and mesopores (whose share in the total volume of the pores of the material is 0.60 to 0.97). The presence of micropores due to the presence of highly dispersed fragments of microporous crystalline silicates, homogeneous distributed in the volume of the mesoporous phase formed stereoregular system mesopores. As a result, the catalyst micro-mesoporous structure combines the advantages of a microporous crystalline zeolite (the presence of acid sites with the activation energy of desorption of ammonia 140-190 kJ/mol, which share in the total spectrum of acidity is not less than 0.5) and mesoporous molecular sieves (developed regular porous structure with a pore volume of not less than 0.45 cm3/g).

To obtain micro-mesoporous catalysts were used microporous crystalline silicates different crystal structures and different chemical composition, properties presented in table 1.

Table 1
StructureCompositionPore volume, cm3/gThe proportion of microporesα*
1MORAl2O3·97SiO2of € 0.1951,00,53
2WEAHAl2O3·84SiO20,1841,00,70
3MFIAl2O3·80SiO20,1641,00,70
*α - the proportion of acid sites with the activation energy of desorption of ammonia 140-190 kJ/mol in the total spectrum of acidity

As the source of microporous zeolites are used industrially available mordenite with respect to SiO2/Al2O3=97 (MOR), beta with respect to SiO2/Al2O3=84 (BEA) and ZSM-5 with the ratio of SiO2/Al2O3=80 (MFI). Synthesis of mesoporous catalyst MCM-41 with respect to SiO2/Al2O3=90 carried out using as a template of cetyltrimethylammonium bromide at 105°C for 48 hours under hydrothermal conditions in accordance with C.T.Kresge, M.E.Leonowicz et al. // Nature, 359 (1992) 710.

The hydrocarbon conversion is carried out in a continuous flow reactor with a fixed bed of the catalyst composition according to the invention in the temperature range from 220 to 550°s at a gauge pressure of from 0.1 to 1 MPa, the feed rate of the raw material is from 0.5 to 5 the/g· h in the presence of inert gas. The hydrocarbon conversion is selected from a number of processes involving the cracking of 1,3,5-triisopropylbenzene; alkylation of polynuclear aromatic compounds such as biphenyl; transalkylation biphenyl and diisopropylbenzene; acylation of benzene dodecanol acid; octane isomerization, oligomerization of propylene and conversion of propane to aromatics. The composition of the reaction products was determined chromatographically.

The following examples illustrate the invention but do not restrict it.

Example 1.

Micro-mesoporous catalyst (ReMOR) is prepared as follows: 30 ml of 0.2 mol/l NaOH solution add 5 g of microporous crystalline aluminosilicate structure of mordenite. The resulting suspension is stirred at room temperature for 2 h, then mixed with solution 7,76 g hexadecyltrimethylammonium (C16H33(CH3)3NBr) in 48 ml of H2O. To the resulting mixture add 10 ml of 2 mol/l hydrochloric acid to form a gel with a pH of 7.5. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 24 h at 110°C. after the hydrothermal treatment, the material is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined PR is 550° C for 24 h In the result of micro-mesoporous catalyst with a zeolite structure of mordenite with a pore volume 0,823 cm3/g, with shares of micropores and mesopores in the pore volume of 0.03 and 0.97, respectively.

Example 2.

The cracking of 1,3,5-triisopropylbenzene is as follows: micro-mesoporous catalyst described in example 1 is placed in a flow reactor, rinsed with nitrogen at a temperature of 550°With, then reduce temperature to 300°and serves 1,3,5-triisopropylbenzene at a pressure of 0.1 MPa, feed rate of 1 g/g·h, diluted with nitrogen in a ratio of 1,3,5-triisopropylbenzene: N2=1:5 (mol). The results of the experiment are presented in table 2.

Example 3.

Similar to example 2, the difference is that the use of microporous catalyst MOR. The results of the experiment are presented in table 2.

Example 4.

Similar to example 2, the difference is that the use mesoporous catalyst MCM-41. The results of the experiment are presented in table 2.

Example 5.

The catalyst was prepared analogously to example 1, but 5 g of microporous crystalline aluminosilicate structure of mordenite added to 30 ml of 0.5 mol/l NaOH solution. The result is a micro-mesoporous catalyst with the structure of a zeolite of mordenite, pore volume 0,365 cm3/g, with shares of micropores and mesopores in the pore volume of 0.40 and 0,0 respectively.

Example 6.

Transalkylation biphenyl p-diisopropylbenzene is as follows: micro-mesoporous catalyst described in example 5 is placed in a flow reactor, rinsed with nitrogen at a temperature of 400°With, then reduce the temperature to 220°and serves biphenyl with p-diisopropylbenzene at a pressure of 1 MPa, feed speed biphenyl 0.5 g/g·h, molar ratio biphenyl : p-diisopropylbenzene : N2=1:6:10. The results of the experiment are presented in table 2.

Example 7.

Similar to example 6, the difference is that the use of microporous catalyst MOR. The results of the experiment are presented in table 2.

Example 8.

Similar to example 6, the difference is that the use mesoporous catalyst MCM-41. The results of the experiment are presented in table 2.

Example 9.

The alkylation of biphenyl with propylene is carried out as follows: micro-mesoporous catalyst described in example 5 is placed in a flow reactor, rinsed with nitrogen at a temperature of 400°With, then reduce the temperature to 220°and serves biphenyl with propylene at a pressure of 1 MPa, feed speed biphenyl 0.5 g/g·h, molar ratio biphenyl : propylene : N2=1:6:10. The results of the experiment are presented in table 2.

Example 10.

Similar to example 9, the difference is that using mi is rapacity catalyst MOR. The results of the experiment are presented in table 2.

Example 11.

Similar to example 9, the difference is that the use mesoporous catalyst MCM-41. The results of the experiment are presented in table 2.

Example 12.

Alkylation of benzene with dodecene-1 is as follows: micro-mesoporous catalyst described in example 5 is placed in a flow reactor, rinsed with nitrogen at a temperature of 550°With, then reduce the temperature to 230°and serves a mixture of benzene with dodecene-1 at a pressure of 0.1 MPa, the feed rate of raw materials 3.7 g/g·h, molar ratio of benzene : dodecen-1 = 1:8. The velocity of the gas diluent N210 ml/min the results of the experiment are presented in table 2.

Example 13.

Similar to example 9, the difference is that the use of microporous catalyst MOR. The results of the experiment are presented in table 2.

Example 14.

Similar to example 9, the difference is that the use mesoporous catalyst MCM-41. The results of the experiment are presented in table 2.

Example 15.

Acylation of benzene dodecanol acid is carried out as follows: micro-mesoporous catalyst described in example 5 is placed in a flow reactor, rinsed with nitrogen at a temperature of 550°With, then reduce the temperature to 230°and submit a solution dodecanol acid in benzene (mol the NYM ratio of benzene : acid=30:1 at a speed of 5 g/g· h at a pressure of 0.1 MPa. Speed N210-30 ml/min the results of the experiment are presented in table 2.

Example 16.

Similar to example 12, the difference is that the use of microporous catalyst MOR. The results of the experiment are presented in table 2.

Example 17.

Similar to example 12, the difference is that the use mesoporous catalyst MCM-41. The results of the experiment are presented in table 2.

Example 18.

Micro-mesoporous catalyst (ReBEA) is prepared as follows: 30 ml of 0.75 mol/l NaOH solution add 5 g of microporous crystalline aluminosilicate structure WEAH. The resulting suspension is stirred at room temperature for 1 h, and then mixed with a solution of 6,56 g dodecyltrimethylammonium (C12H25(CH3)3HBr) in 48 ml of N2O. To the resulting mixture add 10 ml of 2 mol/l hydrochloric acid to form a gel with a pH of 9.0. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 72 h at 100°C. after the hydrothermal treatment, the material is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined at 550°within 24 hours the result of micro-mesoporous catalyst with a zeolite structure by BEA with the volume of pores 0,415 cm3

Examples 19-21 illustrate the catalytic properties of the catalysts in the isomerization of n-octane. For carrying out the isomerization process in the catalyst should be present platinum, creating additional active centers. Modification of microporous, micro-and mesoporous mesoporous catalysts were carried out by ion exchange in a solution of salt [Pt(NH3)4]Cl2taken in quantity 1/580 by weight of the catalyst for 3 hours at room temperature followed by washing, drying at 100°C, calcination and reduction with hydrogen at 400°C. All catalysts contain 0.1 wt.% Pt.

Example 19.

Isomerisation of n-octane is carried out in the presence of micro-mesoporous catalyst described in example 15, containing 0.1 wt.% Pt, as follows: the catalyst is placed in a flow reactor, rinsed in a stream of hydrogen at a temperature of 400°C for 1 h, then reduce the temperature to 230°and serves octane at the rate of 2 g/g·h at a pressure of 0.1 MPa, and a molar ratio of H2: octane=5:1. The results of the experiment are presented in table 2.

Example 20.

Similar to example 16, the difference is that the use of microporous catalyst WEAH, containing 0.1 wt.% Pt. The results of the experiment PR is dstanley in table 2.

Example 21.

Similar to example 16, the difference is that the use mesoporous catalyst MCM-41 containing 0.1 wt.% Pt. The results of the experiment are presented in table 2.

Example 22.

Micro-mesoporous catalyst (ReBEA) is prepared as follows: 30 ml of 1.5 mol/l NaOH solution add 5 g of microporous crystalline aluminosilicate structure WEAH. The resulting suspension is stirred at room temperature for 1 h, and then mixed with solution 7,16 g octadecyltrimethylammonium (C18H37(CH3)3NBr) in 48 ml of N2O. To the resulting mixture add 10 ml of 2 mol/l hydrochloric acid to form a gel with a pH=8. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 10 h at 150°C. after the hydrothermal treatment, the material is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined at 550°within 24 hours the result of micro-mesoporous catalyst with a pore volume 0,427 cm3/g, with shares of micropores and mesopores in the pore volume of 0.27 and 0.73, respectively.

Example 23.

Oligomerization of propylene is carried out as follows: micro-mesoporous catalyst described in example 19, is placed in a flow reactor, rinsed in a stream of nitrogen while the temperature is e 500° With, then reduce temperature to 350°and serves propylene with a speed of 3 g/g·h at a pressure of 0.1 MPa. The results of the experiment are presented in table 2.

Example 24.

Analogous to example 20, the difference is that the use of microporous catalyst WEAH. The results of the experiment are presented in table 2.

Example 25.

Analogous to example 20, the difference is that the use mesoporous catalyst MCM-41. The results of the experiment are presented in table 2.

Example 26.

Micro-mesoporous catalyst (ReMFI) is prepared as follows: 30 ml of 0.5 mol/l NaOH solution add 5 g of microporous crystalline aluminosilicate with the MFI structure. The resulting suspension is stirred at room temperature for 1 h, and then mixed with solution 7,76 g hexadecyltrimethylammonium (C16H33(CH3)3HBr) in 48 ml of N2O. To the resulting mixture add 10 ml of 2 mol/l hydrochloric acid to form a gel with a pH=8. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 24 h at 110°C. after the hydrothermal treatment, the material is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined at 550°within 24 hours the result of micro-mesoporous catalyst is a zeolite of the MFI structure, with the volume of pores 0,510 cm3/g, with shares of micropores and mesopores in the pore volume of 0.20 and 0.80, respectively.

Examples 27-29 illustrate the catalytic properties of the catalysts in the process of aromatization of propane. For carrying out the isomerization process in the catalyst should be present zinc, creating additional active centers. Modification of microporous, micro-and mesoporous mesoporous catalysts were carried out by impregnation of the catalyst salt solution of Zn(NO3)2·6N2O, taken in the amount of 1/2,1 by weight of the catalyst, at room temperature, followed by drying at 100°and annealing at 500°C. All catalysts containing 2 wt.% Zn.

Example 27.

Aromatization of propane is as follows: micro-mesoporous catalyst described in example 23 containing 2 wt.% Zn, placed in a flow reactor, rinsed in a stream of dry air at a temperature of 550°and serves propane at the rate of 2 g/g·h at a pressure of 0.1 MPa. The results of the experiment are presented in table 2.

Example 28.

Similar to example 24, the difference is that the use of microporous MFI catalyst containing 2 wt.% Zn. The results of the experiment are presented in table 2.

Example 29.

Similar to example 24, the difference is that the use mesoporous catalyst M Is M-41, containing 2 wt.% Zn. The results of the experiment are presented in table 2.

Example 30.

Micro-mesoporous catalyst (ReMOR) is prepared as follows: 30 ml of 1.0 mol/l NaOH solution add 5 g of microporous crystalline gelatoria with MOR structure. The resulting suspension is stirred at room temperature for 2 h, then mixed with solution 7,76 g dodecyltrimethylammonium (C12H25(CH3)3NBr) in 48 ml of N2O. To the resulting mixture is added 15 ml of 2 mol/l hydrochloric acid to form a gel with a pH=8. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 48 h at 110°C. after the hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined at 550°within 24 hours the result is a material with the structure of the MOR zeolite, the ratio of SiO2/Fe2O3=20, pore volume of 0.50 cm3/g, with shares of micropores and mesopores in the pore volume of 0.20 and 0.80, respectively. The proportion of acid sites with the activation energy of desorption of ammonia 140-190 kJ/mol in the total spectrum of acidity is 0.70.

Example 31.

Similar to example 2, the difference is that the use of micro-mesoporous catalyst described in example 30. The results of exp is riment presented in table 2.

Example 32.

Similar to example 2, the difference is that the use of microporous iron-containing catalyst with the structure of MOR (FeMOR). The results of the experiment are presented in table 2.

Example 33.

Similar to example 2, the difference lies in the fact that the use of mesoporous iron-containing catalyst with the structure of MCM-41 (FeMCM-41). The results of the experiment are presented in table 2.

Example 34.

Micro-mesoporous material is prepared as follows: 30 ml of 10 mol/l NaOH solution add 5 microporous crystalline of zhelezohromovye with the structure of zeolite MOR. The resulting suspension is stirred at room temperature recepie 2 hours, then mixed with solution 7,76 g of cetyltrimethylammonium bromide (C16H33(CH3)3NBr) in 48 ml of H2O. To the resulting mixture add 10 ml of 2 mol/l hydrochloric acid to form a gel with a pH=8. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 24 h at 110°C. after the hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined at 550°within 24 hours the result is the catalyst with the structure of a zeolite of mordenite (MOR) composition of Al2O3·Fe2O3·50SiO2that is the volume of pores of 0.65 cm 3/g, with shares of micropores and mesopores in the pore volume of 0.30 and 0.70, respectively. The proportion of acid sites with the activation energy of descrbie ammonia 140-190 kJ/mol in the total spectrum of acidity is 0.70.

Example 35.

Similar to example 2, the difference is that the use of micro-mesoporous catalyst described in example 34. The results of the experiment are presented in table 2.

Example 36.

Similar to example 2, the difference is that the use of microporous iron-containing catalyst with MOR structure (Fe, polygraphic plant). The results of the experiment are presented in table 2.

Example 37.

Similar to example 2, the difference lies in the fact that the use of mesoporous iron-containing catalyst with the structure of MCM-41 (Fe, AlMCM-41). The results of the experiment are presented in table 2.

Example 38.

Micro-mesoporous catalyst is prepared as follows: 30 ml of 1.5 mol/l NaOH solution add 5 g of microporous crystalline gallosilikata with the structure of zeolite BEA. The resulting suspension is stirred at room temperature for 2 h, then mixed with a solution of 8.40 g of octadecyltrimethylammonium (C18H37(CH3)3NBr) in 48 ml of N2O. To the resulting mixture add 10 ml of 2 mol/l hydrochloric acid to form a gel with a pH=8. After homogenizing the gel for 1 h, it is transferred into Wroclaw, which is closed and heated for 24 h at 110°C. after the hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 150°C for 24 h and calcined at 550°within 24 hours the result is the catalyst structure of zeolite BEA, with the ratio of SiO2/Ga2O3=50, pore volume of 0.45 cm3/g, with shares of micropores and mesopores in the pore volume of 0.38 and 0.62, respectively. The proportion of acid sites with the activation energy of desorption of ammonia 140-190 kJ/mol in the total spectrum of acidity is 0.60.

Example 39.

Similar to example 2, the difference is that the use of micro-mesoporous catalyst described in example 38. The results of the experiment are presented in table 2.

Example 40.

Similar to example 2, the difference is that the use of microporous iron-containing catalyst with the structure of zeolite BEA (GaBEA). The results of the experiment are presented in table 2.

Example 41.

Similar to example 2, the difference lies in the fact that the use of mesoporous iron-containing catalyst with the structure of MCM-41 (GaMCM-41). The results of the experiment are presented in table 2.

Example 42.

Micro-mesoporous catalyst is prepared as follows: 30 ml of 1.5 mol/l of KOH solution add 5 g of microporous crystalline titanvolume the Licata with BEA structure. The resulting suspension is stirred at room temperature for 2 h, then mixed with solution 7,76 g of cetyltrimethylammonium bromide (C16H33(CH3)3NBr) in 48 ml of N2O. To the resulting mixture is added 15 ml of 2 mol/l hydrochloric acid to form a gel with a pH=8. After homogenizing the gel for 1 h, it is transferred into the autoclave, which is closed and heated for 24 h at 150°C. after the hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 100°C for 24 h and calcined at 550°within 24 hours the result is the catalyst structure of zeolite BEA composition of Al2About3·TiO2·70SiO2, pore volume of 0.65 cm3/g, with shares of micropores and mesopores in the pore volume of 0.15 and of 0.85, respectively. The proportion of acid sites with the activation energy of desorption of ammonia 140-190 kJ/mol in the total spectrum of acidity is 0.50.

Example 43.

Similar to example 2, the difference is that the use of micro-mesoporous catalyst described in example 42. The results of the experiment are presented in table 2.

Example 44.

Similar to example 2, the difference is that the use of microporous technologicai catalyst with BEA structure (Ti, AlBEA). The results of the experiment are presented in table 2.

Example 45

Similar to example 2, the difference is that the use mesoporous technologicai the catalyst with the structure of MCM-41 (Ti, AlMCM-41). The results of the experiment are presented in table 2.

Table 2
# exampleCatalystProperties of the catalyst micro-mesoporous structureConversion, %Selectivity, mol.%
pore volume, cm3/gthe proportion of microporesthe proportion of mesopores
2ReMOR0.8230.150.8536.8123.12
3MOR0.1951.007.117.52
4MSM-410.97001.020.7138.82
6ReMOR0.3650.400.6032.1319,34
7MOR0.1951.0012.336.14
8MSM-41 0.97001.014.033.34
9ReMOR0.3650.400.6096.1362.94
10MOR0.1951.0090.0356.04
11MSM-410.97001.095.2320.44
12ReMOR0.3650.400.6099.1510.06
13MOR0.1951.0099.556.46
14MSM-410.97001.074.453.36
15ReMOR0.3650.400.607.874.38
16MOR0.1951.005.173.88
17MSM-410.97001.01.371.38
1 Pt/ReBEA0.4150.340.6672.7963.610
20Pt/BEA0.1841.0044.2950.210
21Pt/MCM-410.97001.009010
23Pt/ReBEA0.4270.270.7370.61132.112
24Pt/BEA0.1841.0065.41128.712
25Pt/MCM-410.97001.048.01124.012
27Zn/ReMFI0.5100.200.8098.11336.914
28Zn/MFI0.1641.0082.51328.114
29Zn/MCM-410.97001.02.4130.114
31FeReMOR0.5000.600.4026.3 128.02
32FeMOR0.4751.005.216.82
33FeMCM-410.98001.014.0125.02
35FeAlReMOR0.4600.600.4031.4125.62
36FeAlMOR0.4301.006.316.12
37FeAlMCM-410.86001.018.2121.52
39GaReBEA0.4500.380.6229.2125.02
40GaBEA0.4501.006.116.42
41GaMCM-410.96001.015.2123.62
43TiAlReBEA0.6500.150.8517.9118.02
44TiAlBEA0.480 1.003.413.62
45TiAlMCM-410.89001.014.4114.62
1- conversion of 1,3,5-triisopropylbenzene,2the selectivity of the formation of diisopropylbenzene,3- conversion of biphenyl,4the selectivity of the formation of diisopropylphenyl,5- conversion of dodecene-1,6the selectivity of the formation of dodecylbenzene,7- conversion dodecanol acid8- exit 1-phenyl-1-dodecane,9- conversion of octane10the selectivity of the formation of products of isomerization,11- conversion of propylene,12- output hexene,13- conversion of propane,14the selectivity for aromatic hydrocarbons.

1. A method of converting hydrocarbons, including the introduction of hydrocarbons in the conversion of hydrocarbons into contact with a catalyst with micro-mesoporous structure comprising a microporous crystalline silicates with a zeolite structure of T2O3(10-1000)SiO2where T - the elements selected from the group consisting of p-elements of group III or d-element IV-VIII group, or mixtures thereof, the micro-mesoporous structure is characterized by the share of micropores from 0.03 to 0.0 and the proportion of mesopores from 0,60 to 0.97.

2. The method according to claim 1, wherein the hydrocarbon conversion is selected from a number of processes involving the cracking of hydrocarbons, alkylation of aromatic compounds, transalkylating aromatic hydrocarbons, paraffin aromatization of hydrocarbons, the acylation of aromatic compounds, isomerization of paraffin hydrocarbons and the oligomerization of olefinic hydrocarbons.

3. The method according to claim 1, wherein the hydrocarbon conversion is conducted at conditions including a temperature of from 220 to 550°s With gauge pressure of from 0.1 to 1 MPa, the feed rate of 0.5 to 5 g/g·h

4. The method according to claim 1, characterized in that the catalyst with micro-mesoporous structure includes a microporous crystalline silicate with a zeolite with structure type FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW.

5. The method according to claim 1, characterized in that the modified catalyst metals selected from d-elements II and VIII groups.

6. The method according to claim 5, characterized in that the content of metals selected from d-elements II and VIII groups is from 0.1 to 2 wt.%.

7. The method according to claim 1, characterized in that the micro-mesoporous structure has an acidic centers with activation energy of desorption of ammonia 140-190 kJ/mol, whose share of the total number of acid sites is not less than 0.5.

8. Catalyst for conversion of hydrocarbons with micro-saporiti structure, including microporous crystalline silicate with a zeolite structure of T2O3(10-1000)SiO2where T - the elements selected from the group consisting of p-elements of group III or d-element IV-VIII group, or mixtures thereof, the micro-mesoporous structure is characterized by the share of micropores from 0.03 to 0.40 and the proportion of mesopores from 0,60 to 0.97.

9. The catalyst according to claim 8, characterized in that the catalyst with micro-mesoporous structure includes a microporous crystalline silicate with a zeolite with structure type FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW.

10. The catalyst according to claim 8, characterized in that it is modified by metals selected from d-elements II and VIII groups.

11. The catalyst according to claim 10, characterized in that the content of metals selected from d-elements II and VIII groups is from 0.1 to 2 wt.%.

12. The catalyst according to claim 8, characterized in that the micro-mesoporous structure has an acidic centers with activation energy of desorption of ammonia 140-190 kJ/mol, whose share of the total number of acid sites is not less than 0.5.

13. The method of producing the catalyst micro-mesoporous structure, including the suspension of microporous crystalline silicates with zeolite structure having the composition of T2O3(10-1000)SiO2where T - the elements selected from the group consisting of p-elements of group III or d-El is having IV-VIII group, or mixtures thereof in an alkaline solution with a concentration of hydroxide ions is 0.2 to 1.5 mol/l to achieve a residual content of the zeolite phase in suspension 3-40 wt.%, introduction to the suspension of the silicate solution of cationic surfactants in the form of a Quaternary salt of alkylamine composition CnH2n+1(CH3)3NAn, where n=12-18, An Is Cl, Br, HSO4-with the subsequent addition of acid to form a gel with a pH of 7.5-9.0 and hydrothermal treatment of the gel with 100-150°at atmospheric pressure or in an autoclave for 10-72 h with the release of the finished product according to item 8.

14. The method according to item 13, characterized in that the microporous crystalline silicate with zeolite structure using FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW.

15. The method according to 14, characterized in that the catalyst additionally modify the ion exchange method or impregnation with salts of metals selected from d-elements II and VIII groups.

16. The method according to item 15, wherein the use of the modifier in the form of metal salts in an amount to provide in the catalyst metals selected from d-elements II and VIII groups in the amount of from 0.1 to 2 wt.%.



 

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